Dilution index

ABSTRACT

This disclosure relates to ethylene interpolymer compositions. Specifically, ethylene interpolymer products having: a Dilution Index (Y d ) greater than 0; total catalytic metal ≥3.0 ppm; ≥0.03 terminal vinyl unsaturations per 100 carbon atoms, and; optionally a Dimensionless Modulus (X d ) greater than 0. The disclosed ethylene interpolymer products have a melt index from about 0.3 to about 500 dg/minute, a density from about 0.869 to about 0.975 g/cm 3 , a polydispersity (M w /M n ) from about 2 to about 25 and a CDBI 50  from about 20% to about 97%. Further, the ethylene interpolymer products are a blend of at least two ethylene interpolymers; where one ethylene interpolymer is produced with a single-site catalyst formulation and at least one ethylene interpolymer is produced with a heterogeneous catalyst formulation.

CROSS REFERENCE TO RELATED PATENT APPLICATION

This application is a continuation of U.S. application Ser. No.16/010,542, filed on Jun. 18, 2018, which is a continuation U.S.application Ser. No. 15/332,202, filed on Oct. 24, 2016, now granted asU.S. Pat. No. 10,035,906 on Jul. 31, 2018, which is a continuation ofU.S. application Ser. No. 14/918,890, filed on Oct. 21, 2015, nowgranted as U.S. Pat. No. 9,512,282 on Dec. 6, 2016, entitled “DilutionIndex”, which claims priority to Canadian Patent Application No. CA2,868,640, filed Oct. 21, 2014, entitled “Solution PolymerizationProcess” which are herein incorporated by reference in their entirety.

FIELD

This disclosure relates to ethylene interpolymer products manufacturedin a continuous solution polymerization process utilizing at least tworeactors employing at least one single-site catalyst formulation and atleast one heterogeneous catalyst formulation to produce ethyleneinterpolymer products having improved properties.

BACKGROUND

Solution polymerization processes are typically carried out attemperatures above the melting point of the ethylene interpolymer beingsynthesized. In a typical solution polymerization process, catalystcomponents, solvent, monomers and hydrogen are fed under pressure to oneor more reactors.

For ethylene homo polymerization, or ethylene copolymerization, reactortemperatures can range from about 80° C. to about 300° C. whilepressures generally range from about 3 MPag to about 45 MPag and theethylene interpolymer produced is dissolved in a solvent. The residencetime of the solvent in the reactor is relatively short, for example,from about 1 second to about 20 minutes. The solution process can beoperated under a wide range of process conditions that allow theproduction of a wide variety of ethylene interpolymers. Post reactor,the polymerization reaction is quenched to prevent furtherpolymerization, by adding a catalyst deactivator, and passivated, byadding an acid scavenger. Once passivated, the polymer solution isforwarded to a polymer recovery operation where the ethyleneinterpolymer product is separated from process solvent, unreactedresidual ethylene and unreacted optional α-olefin(s).

The polymer industry is in constant need of improved ethyleneinterpolymer products in flexible film applications, non-limitingexamples include food packaging, shrink and stretch films. The inventiveethylene interpolymer products disclosed herein have performanceattributes that are advantageous in many film applications. Elaborating,relative to competitive polyethylenes of similar density and melt index,some embodiments of the disclosed ethylene interpolymers afterconverting into films have one or more of: higher stiffness (e.g.,tensile and/or flex modulus); higher toughness properties (e.g. impactand puncture); higher heat deflection temperatures; higher Vicatsoftening point; improved color (WI and YI); higher melt strength, and;improved heat sealing properties (e.g., heat sealing and hot tack).These recited performance attributes are not to be construed aslimiting.

The polymer industry is also in need of improved ethylene interpolymerproducts for rigid applications; non-limiting examples includecontainers, lids, caps and toys, etc. The inventive ethyleneinterpolymer products disclosed herein have performance attributes thatare advantageous in many rigid applications. Elaborating, relative tocompetitive polyethylenes of similar density and melt index, someembodiments of the disclosed ethylene interpolymers have one or more of:higher stiffness (e.g. flexural modulus); higher toughness properties(e.g., ESCR, PENT, IZOD impact, arm impact, Dynatup impact or Charpyimpact resistance); higher melt strength, higher heat deflectiontemperature; higher Vicat softening temperatures, improved color (WI andYI), and; faster crystallization rates (recited performance attributesare not to be construed as limiting).

Further, the polymerization process and catalyst formulations disclosedherein allow the production of ethylene interpolymer products that canbe converted into flexible or rigid manufactured articles that have aunique balance of physical properties (i.e., several end-use propertiescan be balanced (as desired) through multidimensional optimization);relative to comparative polyethylenes of comparable density and meltindex.

SUMMARY OF DISCLOSURE

This Application claims priority to Canadian Patent Application No. CA2,868,640, filed Oct. 21, 2014 and entitled “SOLUTION POLYMERIZATIONPROCESS”.

One embodiment of this disclosure is an ethylene interpolymer productcomprising: (i) a first ethylene interpolymer; (ii) a second ethyleneinterpolymer, and; (iii) optionally a third ethylene interpolymer; wherethe ethylene interpolymer product has a Dilution Index, Y_(d), greaterthan 0.

One embodiment of this disclosure is an ethylene interpolymer productcomprising: (i) a first ethylene interpolymer; (ii) a second ethyleneinterpolymer, and; (iii) optionally a third ethylene interpolymer; wherethe ethylene interpolymer has ≥0.03 terminal vinyl unsaturations per 100carbon atoms.

One embodiment of this disclosure is an ethylene interpolymer productcomprising: (i) a first ethylene interpolymer; (ii) a second ethyleneinterpolymer, and; (iii) optionally a third ethylene interpolymer; wherethe ethylene interpolymer product has ≥3 parts per million (ppm) of atotal catalytic metal.

Further embodiments of this disclosure include ethylene interpolymerproducts comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer; where the ethylene interpolymer product has a DilutionIndex, Y_(d), greater than 0 and ≥0.03 terminal vinyl unsaturations per100 carbon atoms or ≥3 parts per million (ppm) of a total catalyticmetal or a Dimensionless Modulus, X_(d), >0.

Further embodiments of this disclosure include ethylene interpolymerproducts comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer; where the ethylene interpolymer product has ≥0.03 terminalvinyl unsaturations per 100 carbon atoms and ≥3 parts per million (ppm)of a total catalytic metal or a Dimensionless Modulus, X_(d), >0.

One embodiments of this disclosure includes and ethylene interpolymerproduct comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer; where the ethylene interpolymer product has ≥3 parts permillion (ppm) of a total catalytic metal and a Dimensionless Modulus,X_(d), >0.

Further embodiments of this disclosure include ethylene interpolymerproducts comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer; where the ethylene interpolymer product has a DilutionIndex, Y_(d), greater than 0 and ≥0.03 terminal vinyl unsaturations per100 carbon atoms and ≥3 parts per million (ppm) of a total catalyticmetal or a Dimensionless Modulus, X_(d), >0.

Additional embodiments of this disclosure include ethylene interpolymerproducts comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer; where the ethylene interpolymer product has aDimensionless Modulus, X_(d), >0 and ≥3 parts per million (ppm) of atotal catalytic metal and a Dilution Index, Y_(d), greater than 0 or≥0.03 terminal vinyl unsaturations per 100 carbon atoms

One embodiment of this disclosure includes ethylene interpolymerproducts comprising: (i) a first ethylene interpolymer; (ii) a secondethylene interpolymer, and; (iii) optionally a third ethyleneinterpolymer; where the ethylene interpolymer product has a DilutionIndex, Y_(d), greater than 0, a Dimensionless Modulus, X_(d), >0, ≥3parts per million (ppm) of a total catalytic metal and ≥0.03 terminalvinyl unsaturations per 100 carbon atoms.

Additional embodiments include ethylene interpolymer product having amelt index from about 0.3 to about 500 dg/minute, a density from about0.869 to about 0.975 g/cm³, a M_(w)/M_(n) from about 2 to about 25 and aCDBI₅₀ from about 20% to about 98%; where melt index is measuredaccording to ASTM D1238 (2.16 kg load and 190° C.) and density ismeasured according to ASTM D792.

Further embodiments include ethylene interpolymer products comprising:(i) from about 15 to about 60 weight percent of a first ethyleneinterpolymer having a melt index from about 0.01 to about 200 dg/minuteand a density from about 0.855 g/cm³ to about 0.975 g/cm³; (ii) fromabout 30 to about 85 weight percent of a second ethylene interpolymerhaving a melt index from about 0.3 to about 1000 dg/minute and a densityfrom about 0.89 g/cm³ to about 0.975 g/cm³, and; (iii) optionally fromabout 0 to about 30 weight percent of a third ethylene interpolymerhaving a melt index from about 0.5 to about 2000 dg/minute and a densityfrom about 0.89 to about 0.975 g/cm³; where weight percent is the weightof the first, second or third ethylene polymer divided by the weight ofethylene interpolymer product.

Embodiments of this disclosure include ethylene interpolymer productssynthesized in a solution polymerization process. Embodiments of thisdisclosure include ethylene interpolymer products comprising from 0 toabout 10 mole percent of one or more α-olefins.

Further embodiments ethylene interpolymer products where the firstethylene interpolymer is synthesized using a single-site catalystformulation. In other embodiments the second ethylene interpolymer issynthesized using a first heterogeneous catalyst formulation.Embodiments also include ethylene interpolymers where the third ethyleneinterpolymer is synthesized using a first heterogeneous catalystformulation or a second heterogeneous catalyst formulation. The secondethylene interpolymer may also be synthesized using a first in-lineZiegler Natta catalyst formulation or a first batch Ziegler-Nattacatalyst formulation; optionally, the third ethylene interpolymer issynthesized using the first in-line Ziegler Natta catalyst formulationor the first batch Ziegler-Natta catalyst formulation. The optionalthird ethylene interpolymer may be synthesized using a second in-lineZiegler Natta catalyst formulation or a second batch Ziegler-Nattacatalyst formulation.

Embodiments of this disclosure include ethylene interpolymer productshaving ≤1 part per million (ppm) of a metal A; where metal A originatesfrom the single-site catalyst formulation; non-limiting examples ofmetal A include titanium, zirconium or hafnium.

Further embodiments of this disclosure include ethylene interpolymerproducts comprising a metal B and optionally a metal C; where the totalamount of metal B and metal C is from about 3 to about 11 parts permillion (ppm); where metal B originates from a first heterogeneouscatalyst formulation and metal C form an optional second heterogeneouscatalyst formation. Metals B and C are independently selected from thefollowing non-limiting examples: titanium, zirconium, hafnium, vanadium,niobium, tantalum, chromium, molybdenum, tungsten, manganese,technetium, rhenium, iron, ruthenium or osmium.

Additional embodiments of the ethylene interpolymer products of thisdisclosure comprise a first ethylene interpolymer having a firstM_(w)/M_(n), a second ethylene interpolymer having a second M_(w)/M_(n)and an optional third ethylene having a third M_(w)/M_(n); where thefirst M_(w)/M_(n) is lower than the second M_(w)/M_(n) and the thirdM_(w)/M_(n). Embodiments include ethylene interpolymer products wherethe blending of the second ethylene interpolymer and the third ethyleneinterpolymer form an ethylene interpolymer blend having a fourthM_(w)/M_(n); where the fourth M_(w)/M_(n) is not broader than the secondM_(w)/M_(n). Additional ethylene interpolymer product embodiments arecharacterized as having both the second M_(w)/M_(n) and the thirdM_(w)/M_(n) less than about 4.0.

Embodiments include ethylene interpolymer products where the firstethylene interpolymer has a first CDBI₅₀ from about 70 to about 98%, thesecond ethylene interpolymer has a second CDBI₅₀ from about 45 to about98% and the optional third ethylene interpolymer has a third CDBI₅₀ fromabout 35 to about 98%. Additional embodiments include ethyleneinterpolymer products where the first CDBI₅₀ is higher than the secondCDBI₅₀; optionally the first CDBI₅₀ is higher than the third CDBI₅₀.

DESCRIPTION OF FIGURES

The following Figures are presented for the purpose of illustratingselected embodiments of this disclosure; it being understood, that theembodiments shown do not limit this disclosure.

FIG. 1 illustrates a continuous solution polymerization process where anin-line heterogeneous catalyst formulation is employed.

FIG. 2 illustrates a continuous solution polymerization process where abatch heterogeneous catalyst formulation is employed.

FIG. 3 is a plot of Dilution Index (Y_(d)) (Y_(d) has dimensions ofdegrees (°)) and Dimensionless Modulus (X_(d)) for:

-   -   Comparative S (open triangle, Y_(d)=X_(d)=0) is an ethylene        interpolymer comprising an ethylene interpolymer synthesized        using an in-line Ziegler-Natta catalyst in a solution process        (rheological reference);    -   Examples 6, 101, 102, 103, 110, 115, 200, 201 (solid circle,        Y_(d)>0 and X_(d)<0) are ethylene interpolymer products as        described in this disclosure comprising a first ethylene        interpolymer synthesized using a single-site catalyst        formulation and a second ethylene interpolymer synthesized using        an in-line Ziegler-Natta catalyst formulation in a solution        process;    -   Examples 120, 130 and 131 (solid square, Y_(d)>0, X_(d)>0) are        ethylene interpolymer products as described in this disclosure;    -   Comparatives D and E (open diamond, Y_(d)<0, X_(d)>0) are        ethylene interpolymers comprising a first ethylene interpolymer        synthesized using a single-site catalyst formation and a second        ethylene interpolymer synthesized using a batch Ziegler-Natta        catalyst formulation in a solution process, and;    -   Comparative A (open square, Y_(d)>0 and X_(d)<0) is an ethylene        interpolymer comprising a first and second ethylene interpolymer        synthesized using a single-site catalyst formation in a solution        process.

FIG. 4 illustrates a typical Van Gurp Palmen (VGP) plot of phase angle[°] versus complex modulus [kPa].

FIG. 5 plots the Storage modulus (G′) and loss modulus (G″) showing thecross over frequency Ox and the two decade shift in phase angle to reachω_(c) (ω_(c)=0.01 ω_(x)).

FIG. 6 compares the amount of terminal vinyl unsaturations per 100carbon atoms (terminal vinyl/100 C) in the ethylene interpolymerproducts of this disclosure (solid circles) with Comparatives B, C, E,E2, G, H, H2, I and J (open triangles).

FIG. 7 compares the amount of total catalytic metal (ppm) in theethylene interpolymer products of this disclosure (solid circles) withComparatives B, C, E, E2, G, H, H2, I and J (open triangles).

DEFINITION OF TERMS

Other than in the examples or where otherwise indicated, all numbers orexpressions referring to quantities of ingredients, extrusionconditions, etc., used in the specification and claims are to beunderstood as modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that can vary depending upon the desired properties thatthe various embodiments desire to obtain. At the very least, and not asan attempt to limit the application of the doctrine of equivalents tothe scope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques. The numerical values set forth inthe specific examples are reported as precisely as possible. Anynumerical values, however, inherently contain certain errors necessarilyresulting from the standard deviation found in their respective testingmeasurements.

It should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

All compositional ranges expressed herein are limited in total to and donot exceed 100 percent (volume percent or weight percent) in practice.Where multiple components can be present in a composition, the sum ofthe maximum amounts of each component can exceed 100 percent, with theunderstanding that, and as those skilled in the art readily understand,that the amounts of the components actually used will conform to themaximum of 100 percent.

In order to form a more complete understanding of this disclosure thefollowing terms are defined and should be used with the accompanyingfigures and the description of the various embodiments throughout.

The term “Dilution Index (Y_(d))” and “Dimensionless Modulus (X_(d))”are based on rheological measurements and are fully described in thisdisclosure.

As used herein, the term “monomer” refers to a small molecule that maychemically react and become chemically bonded with itself or othermonomers to form a polymer.

As used herein, the term “α-olefin” is used to describe a monomer havinga linear hydrocarbon chain containing from 3 to 20 carbon atoms having adouble bond at one end of the chain.

As used herein, the term “ethylene polymer”, refers to macromoleculesproduced from ethylene monomers and optionally one or more additionalmonomers; regardless of the specific catalyst or specific process usedto make the ethylene polymer. In the polyethylene art, the one or moreadditional monomers are called “comonomer(s)” and often includeα-olefins. The term “homopolymer” refers to a polymer that contains onlyone type of monomer. Common ethylene polymers include high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE), very low density polyethylene (VLDPE),ultralow density polyethylene (ULDPE), plastomer and elastomers. Theterm ethylene polymer also includes polymers produced in a high pressurepolymerization processes; non-limiting examples include low densitypolyethylene (LDPE), ethylene vinyl acetate copolymers (EVA), ethylenealkyl acrylate copolymers, ethylene acrylic acid copolymers and metalsalts of ethylene acrylic acid (commonly referred to as ionomers). Theterm ethylene polymer also includes block copolymers which may include 2to 4 comonomers. The term ethylene polymer also includes combinationsof, or blends of, the ethylene polymers described above.

The term “ethylene interpolymer” refers to a subset of polymers withinthe “ethylene polymer” group that excludes polymers produced in highpressure polymerization processes; non-limiting examples of polymersproduced in high pressure processes include LDPE and EVA (the latter isa copolymer of ethylene and vinyl acetate).

The term “heterogeneous ethylene interpolymers” refers to a subset ofpolymers in the ethylene interpolymer group that are produced using aheterogeneous catalyst formulation; non-limiting examples of whichinclude Ziegler-Natta or chromium catalysts.

The term “homogeneous ethylene interpolymer” refers to a subset ofpolymers in the ethylene interpolymer group that are produced usingmetallocene or single-site catalysts. Typically, homogeneous ethyleneinterpolymers have narrow molecular weight distributions, for examplegel permeation chromatography (GPC) M_(w)/M_(n) values of less than 2.8;M_(w) and M_(n) refer to weight and number average molecular weights,respectively. In contrast, the M_(w)/M_(n) of heterogeneous ethyleneinterpolymers are typically greater than the M_(w)/M_(n) of homogeneousethylene interpolymers. In general, homogeneous ethylene interpolymersalso have a narrow comonomer distribution, i.e., each macromoleculewithin the molecular weight distribution has a similar comonomercontent. Frequently, the composition distribution breadth index “CDBI”is used to quantify how the comonomer is distributed within an ethyleneinterpolymer, as well as to differentiate ethylene interpolymersproduced with different catalysts or processes. The “CDBI₅₀” is definedas the percent of ethylene interpolymer whose composition is within 50%of the median comonomer composition; this definition is consistent withthat described in U.S. Pat. No. 5,206,075 assigned to Exxon ChemicalPatents Inc. The CDBI₅₀ of an ethylene interpolymer can be calculatedfrom TREF curves (Temperature Rising Elution Fractionation); the TREFmethod is described in Wild, et al., J. Polym. Sci., Part B, Polym.Phys., Vol. 20 (3), pages 441-455. Typically the CDBI₅₀ of homogeneousethylene interpolymers are greater than about 70%. In contrast, theCDBI₅₀ of α-olefin containing heterogeneous ethylene interpolymers aregenerally lower than the CDBI₅₀ of homogeneous ethylene interpolymers.

It is well known to those skilled in the art, that homogeneous ethyleneinterpolymers are frequently further subdivided into “linear homogeneousethylene interpolymers” and “substantially linear homogeneous ethyleneinterpolymers”. These two subgroups differ in the amount of long chainbranching: more specifically, linear homogeneous ethylene interpolymershave less than about 0.01 long chain branches per 1000 carbon atoms;while substantially linear ethylene interpolymers have greater thanabout 0.01 to about 3.0 long chain branches per 1000 carbon atoms. Along chain branch is macromolecular in nature, i.e., similar in lengthto the macromolecule that the long chain branch is attached to.Hereafter, in this disclosure, the term “homogeneous ethyleneinterpolymer” refers to both linear homogeneous ethylene interpolymersand substantially linear homogeneous ethylene interpolymers.

Herein, the term “polyolefin” includes ethylene polymers and propylenepolymers; non-limiting examples of propylene polymers include isotactic,syndiotactic and atactic propylene homopolymers, random propylenecopolymers containing at least one comonomer and impact polypropylenecopolymers or heterophasic polypropylene copolymers.

The term “thermoplastic” refers to a polymer that becomes liquid whenheated, will flow under pressure and solidify when cooled. Thermoplasticpolymers include ethylene polymers as well as other polymers commonlyused in the plastic industry; non-limiting examples of other polymerscommonly used in film applications include barrier resins (EVOH), tieresins, polyethylene terephthalate (PET), polyamides and the like.

As used herein the term “monolayer film” refers to a film containing asingle layer of one or more thermoplastics.

As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or“hydrocarbyl group” refers to linear or cyclic, aliphatic, olefinic,acetylenic and aryl (aromatic) radicals comprising hydrogen and carbonthat are deficient by one hydrogen.

As used herein, an “alkyl radical” includes linear, branched and cyclicparaffin radicals that are deficient by one hydrogen radical;non-limiting examples include methyl (—CH₃) and ethyl (−CH₂CH₃)radicals. The term “alkenyl radical” refers to linear, branched andcyclic hydrocarbons containing at least one carbon-carbon double bondthat is deficient by one hydrogen radical.

As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyland other radicals whose molecules have an aromatic ring structure;non-limiting examples include naphthylene, phenanthrene and anthracene.An “arylalkyl” group is an alkyl group having an aryl group pendantthere from; non-limiting examples include benzyl, phenethyl andtolylmethyl; an “alkylaryl” is an aryl group having one or more alkylgroups pendant there from; non-limiting examples include tolyl, xylyl,mesityl and cumyl.

As used herein, the phrase “heteroatom” includes any atom other thancarbon and hydrogen that can be bound to carbon. A“heteroatom-containing group” is a hydrocarbon radical that contains aheteroatom and may contain one or more of the same or differentheteroatoms. In one embodiment, a heteroatom-containing group is ahydrocarbyl group containing from 1 to 3 atoms selected from the groupconsisting of boron, aluminum, silicon, germanium, nitrogen,phosphorous, oxygen and sulfur. Non-limiting examples ofheteroatom-containing groups include radicals of imines, amines, oxides,phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines,thioethers, and the like. The term “heterocyclic” refers to ring systemshaving a carbon backbone that comprise from 1 to 3 atoms selected fromthe group consisting of boron, aluminum, silicon, germanium, nitrogen,phosphorous, oxygen and sulfur.

As used herein the term “unsubstituted” means that hydrogen radicals arebounded to the molecular group that follows the term unsubstituted. Theterm “substituted” means that the group following this term possessesone or more moieties that have replaced one or more hydrogen radicals inany position within the group; non-limiting examples of moieties includehalogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxylgroups, amine groups, phosphine groups, alkoxy groups, phenyl groups,naphthyl groups, C₁ to C₁₀ alkyl groups, C₂ to C₁₀ alkenyl groups, andcombinations thereof. Non-limiting examples of substituted alkyls andaryls include: acyl radicals, alkylamino radicals, alkoxy radicals,aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals,alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, arylamino radicals and combinations thereof.

Herein the term “R1” and its superscript form “^(R1)” refers to a firstreactor in a continuous solution polymerization process; it beingunderstood that R1 is distinctly different from the symbol R¹; thelatter is used in chemical formula, e.g. representing a hydrocarbylgroup. Similarly, the term “R2” and it's superscript form “^(R2)” refersto a second reactor, and; the term “R3” and it's superscript form“^(R3)” refers to a third reactor.

As used herein, the term “oligomers” refers to an ethylene polymer oflow molecular weight, e.g., an ethylene polymer with a weight averagemolecular weight (Mw) of about 2000 to 3000 daltons. Other commonly usedterms for oligomers include “wax” or “grease”. As used herein, the term“light-end impurities” refers to chemical compounds with relatively lowboiling points that may be present in the various vessels and processstreams within a continuous solution polymerization process;non-limiting examples include, methane, ethane, propane, butane,nitrogen, CO₂, chloroethane, HCl, etc.

DETAILED DESCRIPTION

Catalysts

Organometallic catalyst formulations that are efficient in polymerizingolefins are well known in the art. In the embodiments disclosed herein,at least two catalyst formulations are employed in a continuous solutionpolymerization process. One of the catalyst formulations comprises atleast one single-site catalyst formulation that produces a homogeneousfirst ethylene interpolymer. The other catalyst formulation comprises atleast one heterogeneous catalyst formulation that produces aheterogeneous second ethylene interpolymer. Optionally a third ethyleneinterpolymer may be produced using the heterogeneous catalystformulation that was used to produce the second ethylene interpolymer,or a different heterogeneous catalyst formulation may be used to producethe third ethylene interpolymer. In the continuous solution process, theat least one homogeneous ethylene interpolymer and the at least oneheterogeneous ethylene interpolymer are solution blended and an ethyleneinterpolymer product is produced.

Single Site Catalyst Formulation

The catalyst components which make up the single site catalystformulation are not particularly limited, i.e., a wide variety ofcatalyst components can be used. One non-limiting embodiment of a singlesite catalyst formulation comprises the following three or fourcomponents: a bulky ligand-metal complex; an alumoxane co-catalyst; anionic activator and optionally a hindered phenol. In Tables 1A, 2A, 3Aand 4A of this disclosure: “(i)” refers to the amount of “component(i)”, i.e., the bulky ligand-metal complex added to R1; “(ii)” refers to“component (ii)”, i.e., the alumoxane co-catalyst; “(iii)” refers to“component (iii)” i.e., the ionic activator, and; “(iv)” refers to“component (iv)”, i.e., the optional hindered phenol.

Non-limiting examples of component (i) are represented by formula (I):(L^(A))_(a)M(PI)_(b)(Q)_(n)  (I)

wherein (L^(A)) represents a bulky ligand; M represents a metal atom; PIrepresents a phosphinimine ligand; Q represents a leaving group; a is 0or 1; b is 1 or 2; (a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equalsthe valance of the metal M.

Non-limiting examples of the bulky ligand L^(A) in formula (I) includeunsubstituted or substituted cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted and/or heteroatomcontaining cyclopentadienyl-type ligands. Additional non-limitingexamples include, cyclopenta-phenanthreneyl ligands, unsubstituted orsubstituted indenyl ligands, benzindenyl ligands, unsubstituted orsubstituted fluorenyl ligands, octahydrofluorenyl ligands,cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenylligands, azulene ligands, pentalene ligands, phosphoyl ligands,phosphinimine, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands,borabenzene ligands and the like, including hydrogenated versionsthereof, for example tetrahydroindenyl ligands. In other embodiments,L^(A) may be any other ligand structure capable of q-bonding to themetal M, such embodiments include both η³-bonding and η⁵-bonding to themetal M. In other embodiments, L^(A) may comprise one or moreheteroatoms, for example, nitrogen, silicon, boron, germanium, sulfurand phosphorous, in combination with carbon atoms to form an open,acyclic, or a fused ring, or ring system, for example, aheterocyclopentadienyl ancillary ligand. Other non-limiting embodimentsfor L^(A) include bulky amides, phosphides, alkoxides, aryloxides,imides, carbolides, borollides, porphyrins, phthalocyanines, corrins andother polyazomacrocycles.

Non-limiting examples of metal M in formula (I) include Group 4 metals,titanium, zirconium and hafnium.

The phosphinimine ligand, PI, is defined by formula (II):(R^(p))₃P=N—  (II)

wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

The leaving group Q is any ligand that can be abstracted from formula(I) forming a catalyst species capable of polymerizing one or moreolefin(s). An equivalent term for Q is an “activatable ligand”, i.e.,equivalent to the term “leaving group”. In some embodiments, Q is amonoanionic labile ligand having a sigma bond to M. Depending on theoxidation state of the metal, the value for n is 1 or 2 such thatformula (I) represents a neutral bulky ligand-metal complex.Non-limiting examples of Q ligands include a hydrogen atom, halogens,C₁₋₂₀ hydrocarbyl radicals, C₁₋₂₀ alkoxy radicals, C₅₋₁₀ aryl oxideradicals; these radicals may be linear, branched or cyclic or furthersubstituted by halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀ alkoxyradicals, C₆₋₁₀ arly or aryloxy radicals. Further non-limiting examplesof Q ligands include weak bases such as amines, phosphines, ethers,carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbonatoms. In another embodiment, two Q ligands may form part of a fusedring or ring system.

Further embodiments of component (i) of the single site catalystformulation include structural, optical or enantiomeric isomers (mesoand racemic isomers) and mixtures thereof of the bulky ligand-metalcomplexes described in formula (I) above.

The second single site catalyst component, component (ii), is analumoxane co-catalyst that activates component (i) to a cationiccomplex. An equivalent term for “alumoxane” is “aluminoxane”; althoughthe exact structure of this co-catalyst is uncertain, subject matterexperts generally agree that it is an oligomeric species that containrepeating units of the general formula (III):(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂  (III)

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alumoxane is methylaluminoxane (or MAO) wherein each R group in formula (III) is a methylradical.

The third catalyst component (iii) of the single site catalyst formationis an ionic activator. In general, ionic activators are comprised of acation and a bulky anion; wherein the latter is substantiallynon-coordinating. Non-limiting examples of ionic activators are boronionic activators that are four coordinate with four ligands bonded tothe boron atom. Non-limiting examples of boron ionic activators includethe following formulas (IV) and (V) shown below;[R⁵]⁺[B(R⁷)₄]⁻  (IV)

where B represents a boron atom, R⁵ is an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ is independently selected fromphenyl radicals which are unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich are unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ is independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and; compounds of formula(V);[(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻  (V)

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen orphosphorus atom, t is 2 or 3 and R⁸ is selected from C₁₋₈ alkylradicals, phenyl radicals which are unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ is as defined above in formula(IV).

In both formula (IV) and (V), a non-limiting example of R⁷ is apentafluorophenyl radical. In general, boron ionic activators may bedescribed as salts of tetra(perfluorophenyl) boron; non-limitingexamples include anilinium, carbonium, oxonium, phosphonium andsulfonium salts of tetra(perfluoro-phenyl)boron with anilinium andtrityl (or triphenylmethylium). Additional non-limiting examples ofionic activators include: triethylammonium tetra(phenyl)-boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(penta-fluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenyl-phosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)-boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)-borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)-borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators include N,N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethylium tetrakispentafluorophenyl borate.

The optional fourth catalyst component of the single site catalystformation is a hindered phenol, component (iv). Non-limiting example ofhindered phenols include butylated phenolic antioxidants, butylatedhydroxytoluene, 2,4-di-tertiarybutyl-6-ethyl phenol, 4,4′-methylenebis(2,6-di-tertiary-butylphenol), 1,3, 5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

To produce an active single site catalyst formulation the quantity andmole ratios of the three or four components, (i) through (iv) areoptimized as described below.

Heterogeneous Catalyst Formulations

A number of heterogeneous catalyst formulations are well known to thoseskilled in the art, including, as non-limiting examples, Ziegler-Nattaand chromium catalyst formulations.

In this disclosure, embodiments include an in-line Ziegler-Nattacatalyst formulation and a batch Ziegler-Natta catalyst formation. Theterm “in-line Ziegler-Natta catalyst formulation” refers to thecontinuous synthesis of a small quantity of active Ziegler-Nattacatalyst and immediately injecting this catalyst into at least onecontinuously operating reactor, wherein the catalyst polymerizesethylene and one or more optional α-olefins to form an ethyleneinterpolymer. The terms “batch Ziegler-Natta catalyst formulation” or“batch Ziegler-Natta procatalyst” refer to the synthesis of a muchlarger quantity of catalyst or procatalyst in one or more mixing vesselsthat are external to, or isolated from, the continuously operatingsolution polymerization process. Once prepared, the batch Ziegler-Nattacatalyst formulation, or batch Ziegler-Natta procatalyst, is transferredto a catalyst storage tank. The term “procatalyst” refers to an inactivecatalyst formulation (inactive with respect to ethylene polymerization);the procatalyst is converted into an active catalyst by adding an alkylaluminum co-catalyst. As needed, the procatalyst is pumped from thestorage tank to at least one continuously operating reactor, where anactive catalyst is formed and polymerizes ethylene and one or moreoptional α-olefins to form an ethylene interpolymer. The procatalyst maybe converted into an active catalyst in the reactor or external to thereactor.

A wide variety of chemical compounds can be used to synthesize an activeZiegler-Natta catalyst formulation. The following describes variouschemical compounds that may be combined to produce an activeZiegler-Natta catalyst formulation. Those skilled in the art willunderstand that the embodiments in this disclosure are not limited tothe specific chemical compound disclosed.

An active Ziegler-Natta catalyst formulation may be formed from: amagnesium compound, a chloride compound, a metal compound, an alkylaluminum co-catalyst and an aluminum alkyl. In Table 1A, 2A, 3A and 4Aof this disclosure: “(v)” refers to “component (v)” the magnesiumcompound; the term “(vi)” refers to the “component (vi)” the chloridecompound; “(vii)” refers to “component (vii)” the metal compound;“(viii)” refers to “component (viii)” alkyl aluminum co-catalyst, and;“(ix)” refers to “component (ix)” the aluminum alkyl. As will beappreciated by those skilled in the art, Ziegler-Natta catalystformulations may contain additional components; a non-limiting exampleof an additional component is an electron donor, e.g., amines or ethers.

A non-limiting example of an active in-line Ziegler-Natta catalystformulation can be prepared as follows. In the first step, a solution ofa magnesium compound (component (v)) is reacted with a solution of thechloride compound (component (vi)) to form a magnesium chloride supportsuspended in solution. Non-limiting examples of magnesium compoundsinclude Mg(R¹)₂; wherein the R¹ groups may be the same or different,linear, branched or cyclic hydrocarbyl radicals containing 1 to 10carbon atoms. Non-limiting examples of chloride compounds include R²Cl;wherein R² represents a hydrogen atom, or a linear, branched or cyclichydrocarbyl radical containing 1 to 10 carbon atoms. In the first step,the solution of magnesium compound may also contain an aluminum alkyl(component (ix)). Non-limiting examples of aluminum alkyl includeAl(R³)₃, wherein the R³ groups may be the same or different, linear,branched or cyclic hydrocarbyl radicals containing from 1 to 10 carbonatoms. In the second step a solution of the metal compound (component(vii)) is added to the solution of magnesium chloride and the metalcompound is supported on the magnesium chloride. Non-limiting examplesof suitable metal compounds include M(X)_(n) or MO(X)_(n); where Mrepresents a metal selected from Group 4 through Group 8 of the PeriodicTable, or mixtures of metals selected from Group 4 through Group 8; Orepresents oxygen, and; X represents chloride or bromide; n is aninteger from 3 to 6 that satisfies the oxidation state of the metal.Additional non-limiting examples of suitable metal compounds includeGroup 4 to Group 8 metal alkyls, metal alkoxides (which may be preparedby reacting a metal alkyl with an alcohol) and mixed-ligand metalcompounds that contain a mixture of halide, alkyl and alkoxide ligands.In the third step a solution of an alkyl aluminum co-catalyst (component(viii)) is added to the metal compound supported on the magnesiumchloride. A wide variety of alkyl aluminum co-catalysts are suitable, asexpressed by formula (VI):Al(R⁴)_(p)(OR⁵)_(q)(X)_(r)  (VI)

wherein the R⁴ groups may be the same or different, hydrocarbyl groupshaving from 1 to 10 carbon atoms; the OR⁵ groups may be the same ordifferent, alkoxy or aryloxy groups wherein R⁵ is a hydrocarbyl grouphaving from 1 to 10 carbon atoms bonded to oxygen; X is chloride orbromide, and; (p+q+r)=3, with the proviso that p is greater than 0.Non-limiting examples of commonly used alkyl aluminum co-catalystsinclude trimethyl aluminum, triethyl aluminum, tributyl aluminum,dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminumbutoxide, dimethyl aluminum chloride or bromide, diethyl aluminumchloride or bromide, dibutyl aluminum chloride or bromide and ethylaluminum dichloride or dibromide.

The process described in the paragraph above, to synthesize an activein-line Ziegler-Natta catalyst formulation, can be carried out in avariety of solvents; non-limiting examples of solvents include linear orbranched C₅ to C₁₂ alkanes or mixtures thereof. To produce an activein-line Ziegler-Natta catalyst formulation the quantity and mole ratiosof the five components, (v) through (ix), are optimized as describedbelow.

Additional embodiments of heterogeneous catalyst formulations includeformulations where the “metal compound” is a chromium compound;non-limiting examples include silyl chromate, chromium oxide andchromocene. In some embodiments, the chromium compound is supported on ametal oxide such as silica or alumina. Heterogeneous catalystformulations containing chromium may also include co-catalysts;non-limiting examples of co-catalysts include trialkylaluminum,alkylaluminoxane and dialkoxyalkylaluminum compounds and the like.

Solution Polymerization Process: In-Line Heterogeneous CatalystFormulation

In a continuous solution polymerization process, process solvent,monomer(s) and a catalyst formulation are continuously fed to a reactorwhere the ethylene interpolymer is formed in solution. In FIG. 1,process solvent 1, ethylene 2 and optional α-olefin 3 are combined toproduce reactor feed stream RF1 which flows into reactor 11 a. In FIG. 1optional streams, or optional embodiments, are denoted with dottedlines. It is not particularly important that combined reactor feedstream RF1 be formed; i.e. reactor feed streams can be combined in allpossible combinations, including an embodiment where streams 1 through 3are independently injected into reactor 11 a. Optionally hydrogen may beinjected into reactor 11 a through stream 4; hydrogen is generally addedto control the molecular weight of the first ethylene interpolymerproduced in reactor 11 a. Reactor 11 a is continuously stirred bystirring assembly 11 b which includes a motor external to the reactorand an agitator within the reactor. In the art, such a reactor isfrequently called a CSTR (Continuously Stirred Tank Reactor).

A single site catalyst formulation is injected into reactor 11 a throughstream 5 e. Single site catalyst component streams 5 d, 5 c, 5 b andoptional 5 a refer to the ionic activator (component (iii)), the bulkyligand-metal complex (component (i)), the alumoxane co-catalyst(component (ii)) and optional hindered phenol (component (iv)),respectively. Single site catalyst component streams can be arranged inall possible configurations, including an embodiment where streams 5 athrough 5 d are independently injected into reactor 11 a. Each singlesite catalyst component is dissolved in a catalyst component solvent.Catalyst component solvents, for component (i) through (iv), may be thesame or different. Catalyst component solvents are selected such thatthe combination of catalyst components does not produce a precipitate inany process stream; for example, precipitation of a single site catalystcomponent in stream 5 e. The optimization of the single site catalystformulation is described below.

Reactor 11 a produces a first exit stream, stream 11 c, containing thefirst ethylene interpolymer dissolved in process solvent, as well asunreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen(if present), active single site catalyst, deactivated single sitecatalyst, residual catalyst components and other impurities (ifpresent). Melt index ranges and density ranges of the first ethyleneinterpolymer produced are described below.

The continuous solution polymerization process shown in FIG. 1 includestwo embodiments where reactors 11 a and 12 a can be operated in seriesor parallel modes. In series mode 100% of stream 11 c (the first exitstream) passes through flow controller 11 d forming stream 11 e whichenters reactor 12 a. In contrast, in parallel mode 100% of stream 11 cpasses through flow controller 11 f forming stream 11 g. Stream 11 gby-passes reactor 12 a and is combined with stream 12 c (the second exitstream) forming stream 12 d (the third exit stream).

Fresh reactor feed streams are injected into reactor 12 a; processsolvent 6, ethylene 7 and optional α-olefin 8 are combined to producereactor feed stream RF2. It is not important that stream RF2 is formed;i.e. reactor feed streams can be combined in all possible combinations,including independently injecting each stream into the reactor.Optionally hydrogen may be injected into reactor 12 a through stream 9to control the molecular weight of the second ethylene interpolymer.Reactor 12 a is continuously stirred by stirring assembly 12 b whichincludes a motor external to the reactor and an agitator within thereactor.

An in-line heterogeneous catalyst formulation is injected into reactor12 a through stream 10 f and a second ethylene interpolymer is formed inreactor 12 a. The components that comprise the in-line heterogeneouscatalyst formulation are introduced through streams 10 a, 10 b, 10 c and10 d. A first heterogeneous catalyst assembly, defined by the conduitsand flow controllers associated with streams 10 a-10 h, is operated asdescribed below. In the case of a Ziegler-Natta catalyst, the firstheterogeneous catalyst assembly produces an efficient in-lineZiegler-Natta catalyst formulation by optimizing the following molarratios: (aluminum alkyl)/(magnesium compound) or (ix)/(v); (chloridecompound)/(magnesium compound) or (vi)/(v); (alkyl aluminumco-catalyst)/(metal compound) or (viii)/(vii), and; (aluminumalkyl)/(metal compound) or (ix)/(vii); as well as the time thesecompounds have to react and equilibrate.

Stream 10 a (stream S1) contains a binary blend of a magnesium compound,component (v) and an aluminum alkyl, component (ix), in process solvent.The upper limit on the (aluminum alkyl)/(magnesium compound) molar ratioin stream 10 a may be about 70, in some cases about 50 and is othercases about 30. The lower limit on the (aluminum alkyl)/(magnesiumcompound) molar ratio may be about 3.0, in some cases about 5.0 and inother cases about 10. Stream 10 b (stream S2) contains a solution of achloride compound, component (vi), in process solvent. Stream 10 b iscombined with stream 10 a and the intermixing of streams 10 a and 10 bproduces a magnesium chloride catalyst support. To produce an efficientin-line Ziegler-Natta catalyst (efficient in olefin polymerization), the(chloride compound)/(magnesium compound) molar ratio is optimized. Theupper limit on the (chloride compound)/(magnesium compound) molar ratiomay be about 4, in some cases about 3.5 and is other cases about 3.0.The lower limit on the (chloride compound)/(magnesium compound) molarratio may be about 1.0, in some cases about 1.5 and in other cases about1.9. The time between the addition of the chloride compound and theaddition of the metal compound (component (vii)) via stream 10 c (streamS3) is controlled; hereafter HUT-1 (the first Hold-Up-Time). HUT-1 isthe time for streams 10 a (stream S1) and 10 b (stream S2) toequilibrate and form a magnesium chloride support. The upper limit onHUT-1 may be about 70 seconds, in some cases about 60 seconds and isother cases about 50 seconds. The lower limit on HUT-1 may be about 5seconds, in some cases about 10 seconds and in other cases about 20seconds. HUT-1 is controlled by adjusting the length of the conduitbetween stream 10 b injection port and stream 10 c injection port, aswell as controlling the flow rates of streams 10 a and 10 b. The timebetween the addition of component (vii) and the addition of the alkylaluminum co-catalyst, component (viii), via stream 10 d (stream S4) iscontrolled; hereafter HUT-2 (the second Hold-Up-Time). HUT-2 is the timefor the magnesium chloride support and stream 10 c to react andequilibrate. The upper limit on HUT-2 may be about 50 seconds, in somecases about 35 seconds and is other cases about 25 seconds. The lowerlimit on HUT-2 may be about 2 seconds, in some cases about 6 seconds andin other cases about 10 seconds. HUT-2 is controlled by adjusting thelength of the conduit between stream 10 c injection port and stream 10 dinjection port, as well as controlling the flow rates of streams 10 a,10 b and 10 c. The quantity of the alkyl aluminum co-catalyst added isoptimized to produce an efficient catalyst; this is accomplished byadjusting the (alkyl aluminum co-catalyst)/(metal compound) molar ratio,or (viii)/(vii) molar ratio. The upper limit on the (alkyl aluminumco-catalyst)/(metal compound) molar ratio may be about 10, in some casesabout 7.5 and is other cases about 6.0. The lower limit on the (alkylaluminum co-catalyst)/(metal compound) molar ratio may be 0, in somecases about 1.0 and in other cases about 2.0. In addition, the timebetween the addition of the alkyl aluminum co-catalyst (stream S4) andthe injection of the in-line Ziegler-Natta catalyst formulation intoreactor 12 a is controlled; hereafter HUT-3 (the third Hold-Up-Time).HUT-3 is the time for stream 10 d to intermix and equilibrate to formthe in-line Ziegler Natta catalyst formulation. The upper limit on HUT-3may be about 15 seconds, in some cases about 10 seconds and is othercases about 8 seconds. The lower limit on HUT-3 may be about 0.5seconds, in some cases about 1 seconds and in other cases about 2seconds. HUT-3 is controlled by adjusting the length of the conduitbetween stream 10 d injection port and the catalyst injection port inreactor 12 a, and by controlling the flow rates of streams 10 a through10 d. As shown in FIG. 1, optionally, 100% of stream 10 d, the alkylaluminum co-catalyst, may be injected directly into reactor 12 a viastream 10 h. Optionally, a portion of stream 10 d may be injecteddirectly into reactor 12 a via stream 10 h and the remaining portion ofstream 10 d injected into reactor 12 a via stream 10 f.

As previously indicated, an equivalent term for reactor 12 a is “R2”.The quantity of in-line heterogeneous catalyst formulation added to R2is expressed as the parts-per-million (ppm) of metal compound (component(vii)) in the reactor solution, hereafter “R2 (vii) (ppm)”. The upperlimit on R2 (vii) (ppm) may be about 10 ppm, in some cases about 8 ppmand in other cases about 6 ppm. The lower limit on R2 (vii) (ppm) insome cases may be about 0.5 ppm, in other cases about 1 ppm and in stillother cases about 2 ppm. The (aluminum alkyl)/(metal compound) molarratio in reactor 12 a, or the (ix)/(vii) molar ratio, is alsocontrolled. The upper limit on the (aluminum alkyl)/(metal compound)molar ratio in the reactor may be about 2, in some cases about 1.5 andis other cases about 1.0. The lower limit on the (aluminum alkyl)/(metalcompound) molar ratio may be about 0.05, in some cases about 0.075 andin other cases about 0.1.

Any combination of the streams employed to prepare and deliver thein-line heterogeneous catalyst formulation to R2 may be heated orcooled, i.e., streams 10 a through 10 h (including stream 10 g (optionalR3 delivery) which is discussed below); in some cases the uppertemperature limit of streams 10 a through 10 g may be about 90° C., inother cases about 80° C. and in still other cases about 70° C. and; insome cases the lower temperature limit may be about 20° C.; in othercases about 35° C. and in still other cases about 50° C.

Injection of the in-line heterogeneous catalyst formulation into reactor12 a produces a second ethylene interpolymer and a second exit stream 12c.

If reactors 11 a and 12 a are operated in a series mode, the second exitstream 12 c contains the second ethylene interpolymer and the firstethylene interpolymer dissolved in process solvent; as well as unreactedethylene, unreacted α-olefins (if present), unreacted hydrogen (ifpresent), active catalysts, deactivated catalysts, catalyst componentsand other impurities (if present). Optionally the second exit stream 12c is deactivated by adding a catalyst deactivator A from catalystdeactivator tank 18A forming a deactivated solution A, stream 12 e; inthis case, FIG. 1 defaults to a dual reactor solution process. If thesecond exit stream 12 c is not deactivated the second exit stream enterstubular reactor 17. Catalyst deactivator A is discussed below.

If reactors 11 a and 12 a are operated in parallel mode, the second exitstream 12 c contains the second ethylene interpolymer dissolved inprocess solvent. The second exit stream 12 c is combined with stream 11g forming a third exit stream 12 d, the latter contains the secondethylene interpolymer and the first ethylene interpolymer dissolved inprocess solvent; as well as unreacted ethylene, unreacted α-olefins (ifpresent), unreacted hydrogen (if present), active catalyst, deactivatedcatalyst, catalyst components and other impurities (if present).Optionally the third exit stream 12 d is deactivated by adding catalystdeactivator A from catalyst deactivator tank 18A forming deactivatedsolution A, stream 12 e; in this case, FIG. 1 defaults to a dual reactorsolution process. If the third exit stream 12 d is not deactivated thethird exit stream 12 d enters tubular reactor 17.

The term “tubular reactor” is meant to convey its conventional meaning,namely a simple tube; wherein the length/diameter (L/D) ratio is atleast 10/1. Optionally, one or more of the following reactor feedstreams may be injected into tubular reactor 17; process solvent 13,ethylene 14 and α-olefin 15. As shown in FIG. 1, streams 13, 14 and 15may be combined forming reactor feed stream RF3 and the latter isinjected into reactor 17. It is not particularly important that streamRF3 be formed; i.e., reactor feed streams can be combined in allpossible combinations. Optionally hydrogen may be injected into reactor17 through stream 16. Optionally, the in-line heterogeneous catalystformulation may be injected into reactor 17 via catalyst stream 10 g;i.e., a portion of the in-line heterogeneous catalyst enters reactor 12a through stream 10 f and the remaining portion of the in-lineheterogeneous catalyst enters reactor 17 through stream 10 g.

FIG. 1 shows an additional embodiment where reactor 17 is supplied witha second heterogeneous catalyst formulation produced in a secondheterogeneous catalyst assembly. The second heterogeneous catalystassembly refers to the combination of conduits and flow controllers thatinclude streams 34 a-34 e and 34 h. The chemical composition of thefirst and second heterogeneous catalyst formulations may be the same, ordifferent. In the case of a Ziegler-Natta catalyst, the secondheterogeneous catalyst assembly produces a second in-line Ziegler-Nattacatalyst formulation. For example, the catalyst components ((v) through(ix)), mole ratios and hold-up-times may differ in the first and secondheterogeneous catalyst assemblies. Relative to the first heterogeneouscatalyst assembly, the second heterogeneous catalyst assembly isoperated in a similar manner, i.e., the second heterogeneous catalystassembly generates an efficient catalyst by optimizing hold-up-times andthe following molar ratios: (aluminum alkyl)/(magnesium compound),(chloride compound)/(magnesium compound), (alkyl aluminumco-catalyst/(metal compound, and (aluminum alkyl)/(metal compound). Tobe clear: stream 34 a contains a binary blend of magnesium compound(component (v)) and aluminum alkyl (component (ix)) in process solvent;stream 34 b contains a chloride compound (component (vi)) in processsolvent; stream 34 c contains a metal compound (component (vii)) inprocess solvent, and; stream 34 d contains an alkyl aluminum co-catalyst(component (viii)) in process solvent. Once prepared, the in-lineZiegler-Natta catalyst is injected into reactor 17 through stream 34 e;optionally, additional alkyl aluminum co-catalyst is injected intoreactor 17 through stream 34 h. As shown in FIG. 1, optionally, 100% ofstream 34 d, the alkyl aluminum co-catalyst, may be injected directlyinto reactor 17 via stream 34 h. Optionally, a portion of stream 34 dmay be injected directly into reactor 17 via stream 34 h and theremaining portion of stream 34 d injected into reactor 17 via stream 34e. In FIG. 1, the first or the second heterogeneous catalyst assemblysupplies 100% of the catalyst to reactor 17. Any combination of thestreams that comprise the second heterogeneous catalyst assembly may beheated or cooled, i.e. streams 34 a-34 e and 34 h; in some cases theupper temperature limit of streams 34 a-34 e and 34 h may be about 90°C., in other cases about 80° C. and in still other cases about 70° C.and; in some cases the lower temperature limit may be about 20° C.; inother cases about 35° C. and in still other cases about 50° C.

In reactor 17 a third ethylene interpolymer may, or may not, form. Athird ethylene interpolymer will not form if catalyst deactivator A isadded upstream of reactor 17 via catalyst deactivator tank 18A. A thirdethylene interpolymer will be formed if catalyst deactivator B is addeddownstream of reactor 17 via catalyst deactivator tank 18B.

The optional third ethylene interpolymer produced in reactor 17 may beformed using a variety of operational modes; with the proviso thatcatalyst deactivator A is not added upstream of reactor 17. Non-limitingexamples of operational modes include: (a) residual ethylene, residualoptional α-olefin and residual active catalyst entering reactor 17 reactto form the optional third ethylene interpolymer, or; (b) fresh processsolvent 13, fresh ethylene 14 and optionally fresh α-olefin 15 are addedto reactor 17 and the residual active catalyst entering reactor 17 formsthe optional third ethylene interpolymer, or; (c) the fresh secondin-line heterogeneous catalyst formulation is added to reactor 17 viastream 10 g or stream 34 e to polymerize residual ethylene and residualoptional α-olefin to form the optional third ethylene interpolymer, or;(d) fresh process solvent 13, ethylene 14, optional α-olefin 15 andfresh second in-line heterogeneous catalyst formulation (10 g or 34 e)are added to reactor 17 to form the optional third ethyleneinterpolymer. Optionally, 100% of the alkyl aluminum co-catalyst may beadded to reactor 17 via stream 34 h, or a portion of the alkyl aluminumco-catalyst may be added to reactor 17 via stream 10 g or 34 h and theremaining portion added via stream 34 h. Optionally fresh hydrogen 16may be added to reduce the molecular weight of the optional thirdoptional ethylene interpolymer.

In series mode, Reactor 17 produces a third exit stream 17 b containingthe first ethylene interpolymer, the second ethylene interpolymer andoptionally a third ethylene interpolymer. As shown in FIG. 1, catalystdeactivator B may be added to the third exit stream 17 b via catalystdeactivator tank 18B producing a deactivated solution B, stream 19; withthe proviso that catalyst deactivator B is not added if catalystdeactivator A was added upstream of reactor 17. Deactivated solution Bmay also contain unreacted ethylene, unreacted optional α-olefin,unreacted optional hydrogen and impurities if present. As indicatedabove, if catalyst deactivator A was added, deactivated solution A(stream 12 e) exits tubular reactor 17 as shown in FIG. 1.

In parallel mode operation, reactor 17 produces a fourth exit stream 17b containing the first ethylene interpolymer, the second ethyleneinterpolymer and optionally a third ethylene interpolymer. As indicatedabove, in parallel mode, stream 12 d is the third exit stream. As shownin FIG. 1, in parallel mode, catalyst deactivator B is added to thefourth exit stream 17 b via catalyst deactivator tank 18B producing adeactivated solution B, stream 19; with the proviso that catalystdeactivator B is not added if catalyst deactivator A was added upstreamof reactor 17.

In FIG. 1, deactivated solution A (stream 12 e) or B (stream 19) passesthrough pressure let down device 20, heat exchanger 21 and a passivatoris added via tank 22 forming a passivated solution 23; the passivator isdescribed below. The passivated solution passes through pressure letdown device 24 and enters a first vapor/liquid separator 25. Hereafter,“V/L” is equivalent to vapor/liquid. Two streams are formed in the firstV/L separator: a first bottom stream 27 comprising a solution that isrich in ethylene interpolymers and also contains residual ethylene,residual optional α-olefins and catalyst residues, and; a first gaseousoverhead stream 26 comprising ethylene, process solvent, optionalα-olefins, optional hydrogen, oligomers and light-end impurities ifpresent.

The first bottom stream enters a second V/L separator 28. In the secondV/L separator two streams are formed: a second bottom stream 30comprising a solution that is richer in ethylene interpolymer and leanerin process solvent relative to the first bottom stream 27, and; a secondgaseous overhead stream 29 comprising process solvent, optionalα-olefins, ethylene, oligomers and light-end impurities if present.

The second bottom stream 30 flows into a third V/L separator 31. In thethird V/L separator two streams are formed: a product stream 33comprising an ethylene interpolymer product, deactivated catalystresidues and less than 5 weight % of residual process solvent, and; athird gaseous overhead stream 32 comprised essentially of processsolvent, optional α-olefins and light-end impurities if present.

Product stream 33 proceeds to polymer recovery operations. Non-limitingexamples of polymer recovery operations include one or more gear pump,single screw extruder or twin screw extruder that forces the moltenethylene interpolymer product through a pelletizer. A devolatilizingextruder may be used to remove small amounts of residual process solventand optional α-olefin, if present. Once pelletized the solidifiedethylene interpolymer product is typically dried and transported to aproduct silo.

The first, second and third gaseous overhead streams shown in FIG. 1(streams 26, 29 and 32, respectively) are sent to a distillation columnwhere solvent, ethylene and optional α-olefin are separated forrecycling, or; the first, second and third gaseous overhead streams arerecycled to the reactors, or; a portion of the first, second and thirdgaseous overhead streams are recycled to the reactors and the remainingportion is sent to a distillation column.

Solution Polymerization Process: Batch Heterogeneous CatalystFormulation

In FIG. 2 a first batch heterogeneous catalyst assembly (vessels andstreams 60 a through 60 h) and an optional second batch heterogeneouscatalyst assembly (vessels and streams 90 a through 90 f) are employed.For the sake of clarity and avoid any confusion, many of the vessels andstreams shown in FIG. 2 are equivalent to the respective vessel andstream shown in FIG. 1; equivalence is indicated through the use of aconsistent vessel or stream label, i.e., number. For the avoidance ofdoubt, referring to FIG. 2, process solvent is injected into CSTRreactor 11 a, CSTR reactor 12 a and tubular reactor 17 via streams 1, 6and 13. Ethylene is injected into reactors 11 a, 12 a and 17 via streams2, 7 and 14. Optional α-olefin is injected into reactors 11 a, 12 a and17 via streams 3, 8 and 15. Optional hydrogen is injected into reactors11 a, 12 a and 17 via streams 4, 9 and 16. A single-site catalystformulation is injected into reactor 11 a, producing the first ethyleneinterpolymer. Single-site catalyst component streams (5 a through 5 e)were described above. A batch Ziegler-Natta catalyst formulation or abatch Ziegler-Natta procatalyst is injected into reactor 12 a via stream60 e and the second ethylene interpolymer is formed. Reactors 11 a and12 a shown in FIG. 2 may be operated in series or parallel modes, asdescribed in FIG. 1 above.

Processes to prepare batch heterogeneous procatalysts and in batchZiegler-Natta procatalysts are well known to those skilled in the art. Anon-limiting formulation useful in the continuous solutionpolymerization process may be prepared as follows. A batch Ziegler-Nattaprocatalyst may be prepared by sequentially added the followingcomponents to a stirred mixing vessel: (a) a solution of a magnesiumcompound (an equivalent term for the magnesium compound is “component(v)”); (b) a solution of a chloride compound (an equivalent term for thechloride compound is “component (vi)”; (c) optionally a solution of analuminum alkyl halide, and; (d) a solution of a metal compound (anequivalent term for the metal compound is “component (vii)”). Suitable,non-limiting examples of aluminum alkyl halides are defined by theformula (R⁶)_(v)AlX_(3-v); wherein the R⁶ groups may be the same ordifferent hydrocarbyl group having from 1 to 10 carbon atoms, Xrepresents chloride or bromide, and; v is 1 or 2. Suitable, non-limitingexamples of the magnesium compound, the chloride compound and the metalcompound were described earlier in this disclosure. Suitable solventswithin which to prepare the procatalyst include linear or branched C₅ toC₁₂ alkanes or mixtures thereof. Individual mixing times and mixingtemperatures may be used in each of steps (a) through (d). The upperlimit on mixing temperatures for steps (a) through (d) in some case maybe 160° C., in other cases 130° C. and in still other cases 100° C. Thelower limit on mixing temperatures for steps (a) through (d) in somecases may be 10° C., in other cases 20° C. and in still other cases 30°C. The upper limit on mixing time for steps (a) through (d) in some casemay be 6 hours, in other cases 3 hours and in still other cases 1 hour.The lower limit on mixing times for steps (a) through (d) in some casesmay be 1 minute, in other cases 10 minutes and in still other cases 30minutes.

Batch Ziegler-Natta procatalyst can have various catalyst component moleratios. The upper limit on the (chloride compound)/(magnesium compound)molar ratio in some cases may be about 3, in other cases about 2.7 andis still other cases about 2.5; the lower limit in some cases may beabout 2.0, in other cases about 2.1 and in still other cases about 2.2.The upper limit on the (magnesium compound)/(metal compound) molar ratioin some cases may be about 10, in other cases about 9 and in still othercases about 8; the lower limit in some cases may be about 5, in othercases about 6 and in still other cases about 7. The upper limit on the(aluminum alkyl halide)/(magnesium compound) molar ratio in some casesmay be about 0.5, in other cases about 0.4 and in still other casesabout 0.3; the lower limit in some cases may be 0, in other cases about0.1 and in still other cases about 0.2. An active batch Ziegler-Nattacatalyst formulation is formed when the procatalyst is combined with analkyl aluminum co-catalyst. Suitable co-catalysts were described earlierin this disclosure. The procatalyst may be activated external to thereactor or in the reactor; in the latter case, the procatalyst and anappropriate amount of alkyl aluminum co-catalyst are independentlyinjected R2 and optionally R3.

Once prepared the batch Ziegler-Natta procatalyst is pumped toprocatalyst storage tank 60 a shown in FIG. 2. Tank 60 a may, or maynot, be agitated. Storage tank 60 c contains an alkyl aluminumco-catalyst; non-limiting examples of suitable alkyl aluminumco-catalysts were described earlier in this disclosure. A batch ZieglerNatta catalyst formulation stream 60 e, that is efficient in convertingolefins to polyolefins, is formed by combining batch Ziegler Nattaprocatalyst stream 60 b (stream S5) with alkyl aluminum co-catalyststream 60 d (stream S4). Stream 60 e is injected into reactor 12 a wherethe second ethylene interpolymer is formed. Operationally, the followingoptions may be employed: (a) 100% of the alkyl aluminum co-catalyst maybe injected into reactor 12 a through stream 60 g, i.e., the batchZiegler-Natta procatalyst is injected into reactor 12 a through stream60 e, or; (b) a portion of the alkyl aluminum co-catalyst is injectedinto reactor 12 a via stream 60 g and the remaining portion passesthrough stream 60 d where it combines with stream 60 b forming the batchZiegler-Natta catalyst formulation which is injected into reactor 12 avia stream 60 e.

Additional optional embodiments, where a batch heterogeneous catalystformulation is employed, are shown in FIG. 2 where: (a) a batchZiegler-Natta procatalyst is injected into tubular reactor 17 throughstream 60 f, or; (b) a batch Ziegler-Natta catalyst formulation isinjected into tubular reactor 17 through stream 60 f. In the case ofoption (a), 100% of the alkyl aluminum co-catalyst is injected directlyinto reactor 17 via stream 60 h. An additional embodiment exists where aportion of the alkyl aluminum co-catalyst flows through stream 60 f andthe remaining portion flows through stream 60 h. Any combination oftanks or streams 60 a through 60 h may be heated or cooled.

FIG. 2 includes additional embodiments where a second batchheterogeneous catalyst assembly, which is defined by vessels and streams90 a through 90 f, may be used to optionally inject a second batchZiegler-Natta catalyst formulation or a second batch Ziegler-Nattaprocatalyst into reactor 17. Once prepared the second batchZiegler-Natta procatalyst is pumped to procatalyst storage tank 90 ashown in FIG. 2. Tank 90 a may, or may not, be agitated. Storage tank 90c contains an alkyl aluminum co-catalyst. A batch Ziegler Natta catalystformulation stream 90 e, that is efficient in converting olefins topolyolefins, is formed by combining the second batch Ziegler Nattaprocatalyst stream 90 b (stream S6) with alkyl aluminum co-catalyststream 90 d (optionally stream). Stream 90 e is optionally injected intoreactor 17, wherein an optional third ethylene interpolymer may beformed. FIG. 2 includes additional embodiments where: (a) the batchZiegler-Natta procatalyst is injected directly into reactor 17 throughstream 90 e and the procatalyst is activated inside reactor 17 byinjecting 100% of the aluminum co-catalyst directly into rector 17 viastream 90 f, or; (b) a portion of the aluminum co-catalyst may flowthrough stream 90 e with the remaining portion flowing through stream 90f. Any combination of tanks or streams 90 a through 90 f may be heatedor cooled.

The time between the addition of the alkyl aluminum co-catalyst (streamS4) and the injection of the batch Ziegler-Natta catalyst formulationinto reactor 12 a is controlled; hereafter HUT-4 (the fourthHold-Up-Time). Referring to FIG. 2, HUT-4 is the time for stream 60 d(stream S4) to intermix and equilibrate with stream 60 b (batchZiegler-Natta procatalyst) to form the batch Ziegler Natta catalystformulation prior to injection into reactor 12 a via in stream 60 e.Optionally, HUT-4 is the time for stream 60 d to intermix andequilibrate with stream 60 b to from the batch Ziegler-Natta catalystformulation prior to injection into the optional third reactor 17 viastream 60 f, or; HUT-4 is the time for stream 90 d to intermix andequilibrate with stream 90 b to form the batch Ziegler-Natta catalystformulation prior to injection into reactor 17 via stream 90 e. Theupper limit on HUT-4 may be about 300 seconds, in some cases about 200seconds and in other cases about 100 seconds. The lower limit on HUT-4may be about 0.1 seconds, in some cases about 1 seconds and in othercases about 10 seconds.

The quantity of batch Ziegler-Natta procatalyst produced and/or the sizeto procatalyst storage tanks 60 a or 90 a is not particularly importantwith respect to this disclosure. However, the large quantity ofprocatalyst produced allows one to operate the continuous solutionpolymerization plant for an extended period of time: the upper limit onthis time in some cases may be about 3 months, in other cases for about2 months and in still other cases for about 1 month; the lower limit onthis time in some cases may be about 1 day, in other cases about 1 weekand in still other cases about 2 weeks.

The quantity of batch Ziegler-Natta procatalyst or batch Ziegler-Nattacatalyst formulation added to reactor 12 a is expressed as “R2 (vii)(ppm)”, i.e., the parts-per-million (ppm) of metal compound (component(vii)) in the reactor solution. The upper limit on R2 (vii) (ppm) may beabout 10 ppm, in some cases about 8 ppm and in other cases about 6 ppm.The lower limit on R2 (vii) (ppm) may be about 0.5 ppm, in some casesabout 1 ppm and in other cases about 2 ppm. The quantity of the alkylaluminum co-catalyst added to reactor 12 a is optimized to produce anefficient catalyst; this is accomplished by adjusting the (alkylaluminum co-catalyst)/(metal compound) molar ratio. The upper limit onthe (alkyl aluminum co-catalyst)/(metal compound) molar ratio may beabout 10, in some cases about 8.0 and is other cases about 6.0. Thelower limit on the (alkyl aluminum co-catalyst)/(metal compound) molarratio may be 0.5, in some cases about 0.75 and in other cases about 1.

Referring to FIG. 2, where the heterogeneous catalyst formulation is abatch Ziegler-Natta catalyst formulation, a third ethylene interpolymermay optionally be formed in reactor 17 by: (a) injecting the first batchZiegler-Natta catalyst formulation or the first batch Ziegler-Nattaprocatalyst into reactor 17 through stream 60 f, or; (b) injecting achemically distinct second batch Ziegler-Natta catalyst formulation orsecond batch Ziegler-Natta procatalyst into reactor 17 through stream 90e. As shown in FIG. 2, the first batch Ziegler-Natta catalystformulation may be deactivated upstream of reactor 17 by adding catalystdeactivator A via deactivator tank 18A to form a deactivated solution A(stream 12 e), or; the first batch Ziegler-Natta catalyst formulationand optionally the second batch Ziegler-Natta catalyst formulation maybe deactivated downstream of reactor 17 by adding catalyst deactivator Bvia deactivator tank 18B to form a deactivated solution B (stream 19).Deactivated solution A or B then pass through pressure let down device20, heat exchange 21 and a passivator may be added via tank 22 formingpassivated solution 23. The remaining vessels (24, 25, 28 and 31) andstreams (26, 27, 29, 39, 32 and 33) and process conditions have beendescribed previously. The ethylene interpolymer product stream 33proceeds to polymer recovery. The first, second and third gaseousoverhead streams shown in FIG. 2 (streams 26, 29 and 32, respectively)are sent to a distillation column where solvent, ethylene and optionalα-olefin are separated for later use, or; the first, second and thirdgaseous overhead streams are recycled to the reactors, or; a portion ofthe first, second and third gaseous overhead streams are recycled to thereactors and the remaining portion is sent to a distillation column.

Optimization of the Single Site Catalyst Formulation

Referring to the embodiments shown in FIGS. 1 and 2; an active singlesite catalyst formulation is produced by optimizing the proportion ofeach of the four single site catalyst components, (i) through (iv). Theterm “active” means the single site catalyst formulation is veryefficient in converting olefins to polyolefins; in practice theoptimization objective is to maximize the following ratio: (pounds ofethylene interpolymer product produced)/(pounds of catalyst consumed).The quantity of bulky ligand metal complex, component (i), added to R1is expressed as the parts per million (ppm) of component (i) in thetotal mass of the solution in R1; hereafter “R1 (i) (ppm)”. The upperlimit on R1 (i) (ppm) may be about 5, in some cases about 3 and is othercases about 2. The lower limit on R1 (i) (ppm) may be about 0.02, insome cases about 0.05 and in other cases about 0.1.

The proportion of catalyst component (iii), the ionic activator, addedto R1 is optimized by controlling the (ionic activator)/(bulkyligand-metal complex) molar ratio in the R1 solution; hereafter “R1(iii)/(i)”. The upper limit on R1 (iii)/(i) may be about 10, in somecases about 5 and in other cases about 2. The lower limit on R1(iii)/(i) may be about 0.1, in some cases about 0.5 and in other casesabout 1.0. The proportion of catalyst component (ii) is optimized bycontrolling the (alumoxane)/(bulky ligand-metal complex) molar ratio inthe R1 solution; hereafter “R1 (ii)/(i)”. The alumoxane co-catalyst isgenerally added in a molar excess relative to the bulky ligand-metalcomplex. The upper limit on R1 (ii)/(i) may be about 1000, in some casesabout 500 and is other cases about 200. The lower limit on R1 (ii)/(i)may be about 1, in some cases about 10 and in other cases about 30.

The addition of catalyst component (iv), the hindered phenol, to R1 isoptional in the embodiments shown in FIGS. 1-2. If added, the proportionof component (iv) is optimized by controlling the (hinderedphenol)/(alumoxane) molar ratio in R1; hereafter “R1 (iv)/(ii)”. Theupper limit on R1 (iv)/(ii) may be about 10, in some cases about 5 andin other cases about 2. The lower limit on R1 (iv)/(ii) may be 0.0, insome cases about 0.1 and in other cases about 0.2.

Any combination of the single site catalyst component streams in FIGS. 1and 2 (streams 5 a-5 e) may, or may not, be heated or cooled. The upperlimit on catalyst component stream temperatures may be about 70° C.; inother cases about 60° C. and in still other cases about 50° C. The lowerlimit on catalyst component stream temperatures may be about 0° C.; inother cases about 20° C. and in still other cases about 40° C.

Additional Solution Polymerization Process Parameters

In the continuous solution processes embodiments shown in FIGS. 1 and 2,a variety of solvents may be used as the process solvent; non-limitingexamples include linear, branched or cyclic C₅ to C₁₂ alkanes.Non-limiting examples of α-olefins include 1-propene, 1-butene,1-pentene, 1-hexene and 1-octene. Suitable catalyst component solventsinclude aliphatic and aromatic hydrocarbons. Non-limiting examples ofaliphatic catalyst component solvents include linear, branched or cyclicC₅₋₁₂ aliphatic hydrocarbons, e.g. pentane, methyl pentane, hexane,heptane, octane, cyclohexane, methylcyclohexane, hydrogenated naphtha orcombinations thereof. Non-limiting examples of aromatic catalystcomponent solvents include benzene, toluene (methylbenzene),ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene(1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures ofxylene isomers, hemellitene (1,2,3-trimethylbenzene), pseudocumene(1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixturesof trimethylbenzene isomers, prehenitene (1,2,3,4-tetramethylbenzene),durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzeneisomers, pentamethylbenzene, hexamethylbenzene and combinations thereof.

It is well known to individuals experienced in the art that reactor feedstreams (solvent, monomer, α-olefin, hydrogen, catalyst formulationetc.) must be essentially free of catalyst deactivating poisons;non-limiting examples of poisons include trace amounts of oxygenatessuch as water, fatty acids, alcohols, ketones and aldehydes. Suchpoisons are removed from reactor feed streams using standardpurification practices; non-limiting examples include molecular sievebeds, alumina beds and oxygen removal catalysts for the purification ofsolvents, ethylene and α-olefins, etc.

Referring to the first and second reactors in FIGS. 1 and 2 anycombination of the CSTR reactor feed streams may be heated or cooled:more specifically, streams 1-4 (reactor 11 a) and streams 6-9 (reactor12 a). The upper limit on reactor feed stream temperatures may be about90° C.; in other cases about 80° C. and in still other cases about 70°C. The lower limit on reactor feed stream temperatures may be about 0°C.; in other cases about 10° C. and in still other cases about 20° C.

Any combination of the streams feeding the tubular reactor may be heatedor cooled; specifically, streams 13-16 in FIGS. 1 and 2. In some cases,tubular reactor feed streams are tempered, i.e., the tubular reactorfeed streams are heated to at least above ambient temperature. The uppertemperature limit on the tubular reactor feed streams in some cases areabout 200° C., in other cases about 170° C. and in still other casesabout 140° C.; the lower temperature limit on the tubular reactor feedstreams in some cases are about 60° C., in other cases about 90° C. andin still other cases about 120° C.; with the proviso that thetemperature of the tubular reactor feed streams are lower than thetemperature of the process stream that enters the tubular reactor.

In the embodiments shown in FIGS. 1 and 2 the operating temperatures ofthe solution polymerization reactors (vessels 11 a (R1) and 12 a (R2))can vary over a wide range. For example, the upper limit on reactortemperatures in some cases may be about 300° C., in other cases about280° C. and in still other cases about 260° C.; and the lower limit insome cases may be about 80° C., in other cases about 100° C. and instill other cases about 125° C. The second reactor, reactor 12 a (R2),is operated at a higher temperature than the first reactor 11 a (R1).The maximum temperature difference between these two reactors(T^(R2)−T^(R1)) in some cases is about 120° C., in other cases about100° C. and in still other cases about 80° C.; the minimum(T^(R2)−T^(R1)) in some cases is about 1° C., in other cases about 5° C.and in still other cases about 10° C. The optional tubular reactor,reactor 17 (R3), may be operated in some cases about 100° C. higher thanR2; in other cases about 60° C. higher than R2, in still other casesabout 10° C. higher than R2 and in alternative cases 0° C. higher, i.e.the same temperature as R2. The temperature within optional R3 mayincrease along its length. The maximum temperature difference betweenthe inlet and outlet of R3 in some cases is about 100° C., in othercases about 60° C. and in still other cases about 40° C. The minimumtemperature difference between the inlet and outlet of R3 is in somecases may be 0° C., in other cases about 3° C. and in still other casesabout 10° C. In some cases R3 is operated an adiabatic fashion and inother cases R3 is heated.

The pressure in the polymerization reactors should be high enough tomaintain the polymerization solution as a single phase solution and toprovide the upstream pressure to force the polymer solution from thereactors through a heat exchanger and on to polymer recovery operations.Referring to the embodiments shown in FIGS. 1 and 2, the operatingpressure of the solution polymerization reactors can vary over a widerange. For example, the upper limit on reactor pressure in some casesmay be about 45 MPag, in other cases about 30 MPag and in still othercases about 20 MPag; and the lower limit in some cases may be about 3MPag, in other some cases about 5 MPag and in still other cases about 7MPag.

Referring to the embodiments shown in FIGS. 1 and 2, prior to enteringthe first V/L separator, the passivated solution (stream 23) may have amaximum temperature in some cases of about 300° C., in other cases about290° C. and in still other cases about 280° C.; the minimum temperaturemay be in some cases about 150° C., in other cases about 200° C. and instill other cases about 220° C. Immediately prior to entering the firstV/L separator the passivated solution in some cases may have a maximumpressure of about 40 MPag, in other cases about 25 MPag and in stillcases about 15 MPag; the minimum pressure in some cases may be about 1.5MPag, in other cases about 5 MPag and in still other cases about 6 MPag.

The first V/L separator (vessel 25 in FIGS. 1 and 2) may be operatedover a relatively broad range of temperatures and pressures. Forexample, the maximum operating temperature of the first V/L separator insome cases may be about 300° C., in other cases about 285° C. and instill other cases about 270° C.; the minimum operating temperature insome cases may be about 100° C., in other cases about 140° C. and instill other cases 170° C. The maximum operating pressure of the firstV/L separator in some cases may be about 20 MPag, in other cases about10 MPag and in still other cases about 5 MPag; the minimum operatingpressure in some cases may be about 1 MPag, in other cases about 2 MPagand in still other cases about 3 MPag.

The second V/L separator (vessel 28 in FIGS. 1 and 2) may be operatedover a relatively broad range of temperatures and pressures. Forexample, the maximum operating temperature of the second V/L separatorin some cases may be about 300° C., in other cases about 250° C. and instill other cases about 200° C.; the minimum operating temperature insome cases may be about 100° C., in other cases about 125° C. and instill other cases about 150° C. The maximum operating pressure of thesecond V/L separator in some cases may be about 1000 kPag, in othercases about 900 kPag and in still other cases about 800 kPag; theminimum operating pressure in some cases may be about 10 kPag, in othercases about 20 kPag and in still other cases about 30 kPag.

The third V/L separator (vessel 31 in FIGS. 1 and 2) may be operatedover a relatively broad range of temperatures and pressures. Forexample, the maximum operating temperature of the third V/L separator insome cases may be about 300° C., in other cases about 250° C., and instill other cases about 200° C.; the minimum operating temperature insome cases may be about 100° C., in other cases about 125° C. and instill other cases about 150° C. The maximum operating pressure of thethird V/L separator in some cases may be about 500 kPag, in other casesabout 150 kPag and in still other cases about 100 kPag; the minimumoperating pressure in some cases may be about 1 kPag, in other casesabout 10 kPag and in still other cases about 25 kPag.

Embodiments of the continuous solution polymerization process shown inFIGS. 1 and 2 show three V/L separators. However, continuous solutionpolymerization embodiments may include configurations comprising atleast one V/L separator.

The ethylene interpolymer products having improved color produced in thecontinuous solution polymerization process may be recovered usingconventional devolatilization systems that are well known to personsskilled in the art, non-limiting examples include flash devolatilizationsystems and devolatilizing extruders.

Any reactor shape or design may be used for reactor 11 a (R1) andreactor 12 a (R2) in FIGS. 1 and 2; non-limiting examples includeunstirred or stirred spherical, cylindrical or tank-like vessels, aswell as tubular reactors or recirculating loop reactors. At commercialscale the maximum volume of R1 in some cases may be about 20,000 gallons(about 75,710 L), in other cases about 10,000 gallons (about 37,850 L)and in still other cases about 5,000 gallons (about 18,930 L). Atcommercial scale the minimum volume of R1 in some cases may be about 100gallons (about 379 L), in other cases about 500 gallons (about 1,893 L)and in still other cases about 1,000 gallons (about 3,785 L). At pilotplant scales reactor volumes are typically much smaller, for example thevolume of R1 at pilot scale could be less than about 2 gallons (lessthan about 7.6 L). In this disclosure the volume of reactor R2 isexpressed as a percent of the volume of reactor R1. The upper limit onthe volume of R2 in some cases may be about 600% of R1, in other casesabout 400% of R1 and in still other cases about 200% of R1. For clarity,if the volume of R1 is 5,000 gallons and R2 is 200% the volume of R1,then R2 has a volume of 10,000 gallons. The lower limit on the volume ofR2 in some cases may be about 50% of R1, in other cases about 100% of R1and in still other cases about 150% of R1. In the case of continuouslystirred tank reactors the stirring rate can vary over a wide range; insome cases from about 10 rpm to about 2000 rpm, in other cases fromabout 100 to about 1500 rpm and in still other cases from about 200 toabout 1300 rpm. In this disclosure the volume of R3, the tubularreactor, is expressed as a percent of the volume of reactor R2. Theupper limit on the volume of R3 in some cases may be about 500% of R2,in other cases about 300% of R2 and in still other cases about 100% ofR2. The lower limit on the volume of R3 in some cases may be about 3% ofR2, in other cases about 10% of R2 and in still other cases about 50% ofR2.

The “average reactor residence time”, a commonly used parameter in thechemical engineering art, is defined by the first moment of the reactorresidence time distribution; the reactor residence time distribution isa probability distribution function that describes the amount of timethat a fluid element spends inside the reactor. The average reactorresidence time can vary widely depending on process flow rates andreactor mixing, design and capacity. The upper limit on the averagereactor residence time of the solution in R1 in some cases may be about600 seconds, in other cases about 360 seconds and in still other casesabout 180 seconds. The lower limit on the average reactor residence timeof the solution in R1 in some cases may be about 10 seconds, in othercases about 20 seconds and in still other cases about 40 seconds. Theupper limit on the average reactor residence time of the solution in R2in some cases may be about 720 seconds, in other cases about 480 secondsand in still other cases about 240 seconds. The lower limit on theaverage reactor residence time of the solution in R2 in some cases maybe about 10 seconds, in other cases about 30 seconds and in still othercases about 60 seconds. The upper limit on the average reactor residencetime of the solution in R3 in some cases may be about 600 seconds, inother cases about 360 seconds and in still other cases about 180seconds. The lower limit on the average reactor residence time of thesolution in R3 in some cases may be about 1 second, in other cases about5 seconds and in still other cases about 10 seconds.

Optionally, additional reactors (e.g., CSTRs, loops or tubes, etc.)could be added to the continuous solution polymerization processembodiments shown in FIGS. 1 and 2. In this disclosure, the number ofreactors is not particularly important; with the proviso that thecontinuous solution polymerization process comprises at least tworeactors that employ at least one single-site catalyst formulation andat least one heterogeneous catalyst formulation.

In operating the continuous solution polymerization process embodimentsshown in FIGS. 1 and 2 the total amount of ethylene supplied to theprocess can be portioned or split between the three reactors R1, R2 andR3. This operational variable is referred to as the Ethylene Split (ES),i.e. “ES^(R1)” “ES^(R2)” and “ES^(R3)” refer to the weight percent ofethylene injected in R1, R2 and R3, respectively; with the proviso thatES^(R1)+ES^(R2)+ES^(R3)=100%. This is accomplished by adjusting theethylene flow rates in the following streams: stream 2 (R1), stream 7(R2) and stream 14 (R3). The upper limit on ES^(R1) in some cases isabout 60%, in other cases about 55% and in still other cases about 50%;the lower limit on ES^(R1) in some cases is about 10%, in other casesabout 15% and in still other cases about 20%. The upper limit on ES^(R2)in some cases is about 90%, in other cases about 80% and in still othercases about 70%; the lower limit on ES^(R2) in some cases is about 20%,in other cases about 30% and in still other cases about 40%. The upperlimit on ES^(R3) in some cases is about 30%, in other cases about 25%and in still other cases about 20%; the lower limit on ES^(R3) in somecases is 0%, in other cases about 5% and in still other cases about 10%.

In operating the continuous solution polymerization process embodimentsshown in FIGS. 1 and 2 the ethylene concentration in each reactor isalso controlled. The R1 ethylene concentration is defined as the weightof ethylene in reactor 1 divided by the total weight of everything addedto reactor 1; the R2 ethylene concentration (wt %) and R3 ethyleneconcentration (wt %) are defined similarly. Ethylene concentrations inthe reactors in some cases may vary from about 7 weight percent (wt %)to about 25 wt %, in other cases from about 8 wt % to about 20 wt % andin still other cases from about 9 wt % to about 17 wt %.

In operating the continuous solution polymerization process embodimentsshown in FIGS. 1 and 2 that produce ethylene interpolymers havingimproved color, the total amount of ethylene converted in each reactoris monitored. The term “Q^(R1)” refers to the percent of the ethyleneadded to R1 that is converted into an ethylene interpolymer by thecatalyst formulation. Similarly Q^(R2) and Q^(R3) represent the percentof the ethylene added to R2 and R3 that was converted into ethyleneinterpolymer, in the respective reactor. Ethylene conversions can varysignificantly depending on a variety of process conditions, e.g.catalyst concentration, catalyst formulation, impurities and poisons.The upper limit on both Q^(R1) and Q^(R2) in some cases is about 99%, inother cases about 95% and in still other cases about 90%; the lowerlimit on both Q^(R1) and Q^(R2) in some cases is about 65%, in othercases about 70% and in still other cases about 75%. The upper limit onQ^(R3) in some cases is about 99%, in other cases about 95% and in stillother cases about 90%; the lower limit on Q^(R3) in some cases is 0%, inother cases about 5% and in still other cases about 10%. The term“Q^(T)” represents the total or overall ethylene conversion across theentire continuous solution polymerization plant; i.e. Q^(T)=100×[weightof ethylene in the interpolymer product]/([weight of ethylene in theinterpolymer product]+[weight of unreacted ethylene]). The upper limiton Q^(T) in some cases is about 99%, in other cases about 95% and instill other cases about 90%; the lower limit on Q^(T) in some cases isabout 75%, in other cases about 80% and in still other cases about 85%.

Optionally, α-olefin may be added to the continuous solutionpolymerization process. If added, α-olefin may be proportioned or splitbetween R1, R2 and R3. This operational variable is referred to as theComonomer Split (CS), i.e. “CS^(R1)”, “CS^(R2)” and “CS^(R3)” refer tothe weight percent of α-olefin comonomer that is injected in R1, R2 andR3, respectively; with the proviso that CS^(R1)+CS^(R2)+CS^(R3)=100%.This is accomplished by adjusting α-olefin flow rates in the followingstreams: stream 3 (R1), stream 8 (R2) and stream 15 (R3). The upperlimit on CS^(R1) in some cases is 100% (i.e. 100% of the α-olefin isinjected into R1), in other cases about 95% and in still other casesabout 90%. The lower limit on CS^(R1) in some cases is 0% (ethylenehomopolymer produced in R1), in other cases about 5% and in still othercases about 10%. The upper limit on CS^(R2) in some cases is about 100%(i.e., 100% of the α-olefin is injected into reactor 2), in other casesabout 95% and in still other cases about 90%. The lower limit on CS^(R2)in some cases is 0%, in other cases about 5% and in still other casesabout 10%. The upper limit on CS^(R3) in some cases is 100%, in othercases about 95% and in still other cases about 90%. The lower limit onCS^(R3) in some cases is 0%, in other cases about 5% and in still othercases about 10%.

Catalyst Deactivation

In the continuous polymerization processes described in this disclosure,polymerization is terminated by adding a catalyst deactivator.Embodiments in FIGS. 1 and 2 show catalyst deactivation occurringeither: (a) upstream of the tubular reactor by adding a catalystdeactivator A from catalyst deactivator tank 18A, or; (b) downstream ofthe tubular reactor by adding a catalyst deactivator B from catalystdeactivator tank 18B. Catalyst deactivator tanks 18A and 18B may containneat (100%) catalyst deactivator, a solution of catalyst deactivator ina solvent, or a slurry of catalyst deactivator in a solvent. Thechemical composition of catalyst deactivator A and B may be the same, ordifferent. Non-limiting examples of suitable solvents include linear orbranched C₅ to C₁₂ alkanes. In this disclosure, how the catalystdeactivator is added is not particularly important. Once added, thecatalyst deactivator substantially stops the polymerization reaction bychanging active catalyst species to inactive forms. Suitabledeactivators are well known in the art, non-limiting examples include:amines (e.g. U.S. Pat. No. 4,803,259 to Zboril et al.); alkali oralkaline earth metal salts of carboxylic acid (e.g., U.S. Pat. No.4,105,609 to Machan et al.); water (e.g., U.S. Pat. No. 4,731,438 toBernier et al.); hydrotalcites, alcohols and carboxylic acids (e.g.,U.S. Pat. No. 4,379,882 to Miyata); or a combination thereof (U.S. Pat.No. 6,180,730 to Sibtain et al.). In this disclosure the quantify ofcatalyst deactivator added was determined by the following catalystdeactivator molar ratio: 0.3≤(catalyst deactivator)/((total catalyticmetal)+(alkyl aluminum co-catalyst)+(aluminum alkyl))≤2.0; where thecatalytic metal is the total moles of (metal A+metal B+optional metalC). The upper limit on the catalyst deactivator molar ratio may be about2, in some cases about 1.5 and in other cases about 0.75. The lowerlimit on the catalyst deactivator molar ratio may be about 0.3, in somecases about 0.35 and in still other cases about 0.4. In general, thecatalyst deactivator is added in a minimal amount such that the catalystis deactivated and the polymerization reaction is quenched.

Solution Passivation

Referring to the embodiments shown in FIGS. 1 and 2; prior to enteringthe first V/L separator, a passivator or acid scavenger is added todeactivated solution A or B to form a passivated solution, i.e.passivated solution stream 23. Passivator tank 22 may contain neat(100%) passivator, a solution of passivator in a solvent, or a slurry ofpassivator in a solvent. Non-limiting examples of suitable solventsinclude linear or branched C₅ to C₁₂ alkanes. In this disclosure, howthe passivator is added is not particularly important. Suitablepassivators are well known in the art, non-limiting examples includealkali or alkaline earth metal salts of carboxylic acids orhydrotalcites. The quantity of passivator added can vary over a widerange. In this disclosure the molar quantity of passivator added wasdetermined by the total moles of chloride compounds added to thesolution process, i.e. the chloride compound “component (vi)” plus themetal compound “compound (vii)”. Optionally, a first and second chloridecompound and a first and second metal compound may be used, i.e. to formthe first and second heterogeneous catalyst formulations; in this casethe amount of passivator added is determined by the total moles allchloride containing compounds. The upper limit on passivator mole ratio(moles passivator)/(total chlorides) molar ratio may be 20, in somecases 15 and in other cases 10. The lower limit on the(passivator)/(total chlorides) molar ratio may be about 5, in some casesabout 7 and in still other cases about 9. In general, the passivator isadded in the minimal amount to substantially passivate the deactivatedsolution.

First Ethylene Interpolymer

The first ethylene interpolymer is produced with a single-site catalystformulation. Referring to the embodiments shown in FIGS. 1 and 2, if theoptional α-olefin is not added to reactor 1 (R1), then the ethyleneinterpolymer produced in R1 is an ethylene homopolymer. If an α-olefinis added, the following weight ratio is one parameter to control thedensity of the first ethylene interpolymer:((α-olefin)/(ethylene))^(R1). The upper limit on((α-olefin)/(ethylene))^(R1) may be about 3; in other cases about 2 andin still other cases about 1. The lower limit on((α-olefin)/(ethylene))^(R1) may be 0; in other cases about 0.25 and instill other cases about 0.5. Hereafter, the symbol “σ¹” refers to thedensity of the first ethylene interpolymer produced in R1. The upperlimit on σ¹ may be about 0.975 g/cm³; in some cases about 0.965 g/cm³and; in other cases about 0.955 g/cm³. The lower limit on σ¹ may beabout 0.855 g/cm³, in some cases about 0.865 g/cm³, and; in other casesabout 0.875 g/cm³.

Methods to determine the CDBI₅₀ (Composition Distribution BranchingIndex) of an ethylene interpolymer are well known to those skilled inthe art. The CDBI₅₀, expressed as a percent, is defined as the percentof the ethylene interpolymer whose comonomer composition is within 50%of the median comonomer composition. It is also well known to thoseskilled in the art that the CDBI₅₀ of ethylene interpolymers producedwith single-site catalyst formulations are higher relative to the CDBI₅₀of α-olefin containing ethylene interpolymers produced withheterogeneous catalyst formulations. The upper limit on the CDBI₅₀ ofthe first ethylene interpolymer (produced with a single-site catalystformulation) may be about 98%, in other cases about 95% and in stillother cases about 90%. The lower limit on the CDBI₅₀ of the firstethylene interpolymer may be about 70%, in other cases about 75% and instill other cases about 80%.

As is well known to those skilled in the art the M_(w)/M_(n) of ethyleneinterpolymers produced with single site catalyst formulations are lowerrelative to ethylene interpolymers produced with heterogeneous catalystformulations. Thus, in the embodiments disclosed, the first ethyleneinterpolymer has a lower M_(w)/M_(n) relative to the second ethyleneinterpolymer; where the second ethylene interpolymer is produced with aheterogeneous catalyst formulation. The upper limit on the M_(w)/M_(n)of the first ethylene interpolymer may be about 2.8, in other casesabout 2.5 and in still other cases about 2.2. The lower limit on theM_(w)/M_(n) the first ethylene interpolymer may be about 1.7, in othercases about 1.8 and in still other cases about 1.9.

The first ethylene interpolymer contains catalyst residues that reflectthe chemical composition of the single-site catalyst formulation used.Those skilled in the art will understand that catalyst residues aretypically quantified by the parts per million of catalytic metal in thefirst ethylene interpolymer, where metal refers to the metal incomponent (i), i.e. the metal in the “bulky ligand-metal complex”;hereafter this metal will be referred to “metal A”. As recited earlierin this disclosure, non-limiting examples of metal A include Group 4metals, titanium, zirconium and hafnium. The upper limit on the ppm ofmetal A in the first ethylene interpolymer may be about 1.0 ppm, inother cases about 0.9 ppm and in still other cases about 0.8 ppm. Thelower limit on the ppm of metal A in the first ethylene interpolymer maybe about 0.01 ppm, in other cases about 0.1 ppm and in still other casesabout 0.2 ppm.

The amount of hydrogen added to R1 can vary over a wide range allowingthe continuous solution process to produce first ethylene interpolymersthat differ greatly in melt index, hereafter I₂ ¹ (melt index ismeasured at 190° C. using a 2.16 kg load following the proceduresoutlined in ASTM D1238). This is accomplished by adjusting the hydrogenflow rate in stream 4 (as shown in FIGS. 1 and 2). The quantity ofhydrogen added to R1 is expressed as the parts-per-million (ppm) ofhydrogen in R1 relative to the total mass in reactor R1; hereafter H₂^(R1) (ppm). In some cases H₂ ^(R1) (ppm) ranges from about 100 ppm to 0ppm, in other cases from about 50 ppm to 0 ppm, in alternative casesfrom about 20 to 0 and in still other cases from about 2 ppm to 0 ppm.The upper limit on I₂ ¹ may be about 200 dg/min, in some cases about 100dg/min; in other cases about 50 dg/min, and; in still other cases about1 dg/min. The lower limit on I₂ ¹ may be about 0.01 dg/min, in somecases about 0.05 dg/min; in other cases about 0.1 dg/min, and; in stillother cases about 0.5 dg/min.

The upper limit on the weight percent (wt %) of the first ethyleneinterpolymer in the ethylene interpolymer product may be about 60 wt %,in other cases about 55 wt % and in still other cases about 50 wt %. Thelower limit on the wt % of the first ethylene interpolymer in theethylene interpolymer product may be about 15 wt %; in other cases about25 wt % and in still other cases about 30 wt %.

Second Ethylene Interpolymer

Referring to the embodiments shown in FIG. 1, if optional α-olefin isnot added to reactor 12 a (R2) either through fresh α-olefin stream 8 orcarried over from reactor 11 a (R1) in stream 11 e (in series mode),then the ethylene interpolymer produced in reactor 12 a (R2) is anethylene homopolymer. If an optional α-olefin is present in R2, thefollowing weight ratio is one parameter to control the density of thesecond ethylene interpolymer produced in R2:((α-olefin)/(ethylene))^(R2). The upper limit on((α-olefin)/(ethylene))^(R2) may be about 3; in other cases about 2 andin still other cases about 1. The lower limit on((α-olefin)/(ethylene))^(R2) may be 0; in other cases about 0.25 and instill other cases about 0.5. Hereafter, the symbol “σ²” refers to thedensity of the ethylene interpolymer produced in R2. The upper limit onσ² may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; inother cases about 0.955 g/cm³. Depending on the heterogeneous catalystformulation used, the lower limit on σ² may be about 0.89 g/cm³, in somecases about 0.90 g/cm³, and; in other cases about 0.91 g/cm³. The rangesdisclosed in this paragraph also apply to the embodiments shown in FIG.2.

A heterogeneous catalyst formulation is used to produce the secondethylene interpolymer. If the second ethylene interpolymer contains anα-olefin, the CDBI₅₀ of the second ethylene interpolymer is lowerrelative to the CDBI₅₀ of the first ethylene interpolymer that wasproduced with a single-site catalyst formulation. In an embodiment ofthis disclosure, the upper limit on the CDBI₅₀ of the second ethyleneinterpolymer (that contains an α-olefin) may be about 70%, in othercases about 65% and in still other cases about 60%. In an embodiment ofthis disclosure, the lower limit on the CDBI₅₀ of the second ethyleneinterpolymer (that contains an α-olefin) may be about 45%, in othercases about 50% and in still other cases about 55%. If an α-olefin isnot added to the continuous solution polymerization process the secondethylene interpolymer is an ethylene homopolymer. In the case of ahomopolymer, which does not contain α-olefin, one can still measure aCDBI₅₀ using TREF. In the case of a homopolymer, the upper limit on theCDBI₅₀ of the second ethylene interpolymer may be about 98%, in othercases about 96% and in still other cases about 95%, and; the lower limiton the CDBI₅₀ may be about 88%, in other cases about 89% and in stillother cases about 90%. It is well known to those skilled in the art thatas the α-olefin content in the second ethylene interpolymer approacheszero, there is a smooth transition between the recited CDBI₅₀ limits forthe second ethylene interpolymers (that contain an α-olefin) and therecited CDBI₅₀ limits for the second ethylene interpolymers that areethylene homopolymers. Typically, the CDBI₅₀ of the first ethyleneinterpolymer is higher than the CDBI₅₀ of the second ethyleneinterpolymer.

The M_(w)/M_(n) of second ethylene interpolymer is higher than theM_(w)/M_(n) of the first ethylene interpolymer. The upper limit on theM_(w)/M_(n) of the second ethylene interpolymer may be about 4.4, inother cases about 4.2 and in still other cases about 4.0. The lowerlimit on the M_(w)/M_(n) of the second ethylene interpolymer may beabout 2.2. M_(w)/M_(n)'s of 2.2 are observed when the melt index of thesecond ethylene interpolymer is high, or when the melt index of theethylene interpolymer product is high, e.g., greater than 10 dg/minute.In other cases the lower limit on the M_(w)/M_(n) of the second ethyleneinterpolymer may be about 2.4 and in still other cases about 2.6.

The second ethylene interpolymer contains catalyst residues that reflectthe chemical composition of the heterogeneous catalyst formulation.Those skilled in the art with understand that heterogeneous catalystresidues are typically quantified by the parts per million of catalyticmetal in the second ethylene interpolymer, where the metal refers to themetal originating from “component (vii)”, i.e., the metal compound;hereafter this metal will be referred to as “metal B”. As recitedearlier in this disclosure, non-limiting examples of metal B includemetals selected from Group 4 through Group 8 of the Periodic Table, ormixtures of metals selected from Group 4 through Group 8. The upperlimit on the ppm of metal B in the second ethylene interpolymer may beabout 12 ppm, in other cases about 10 ppm and in still other cases about8 ppm. The lower limit on the ppm of metal B in the second ethyleneinterpolymer may be about 2 ppm, in other cases about 3 ppm and in stillother cases about 4 ppm. While not wishing to be bound by any particulartheory, in series mode of operation it is believed that the chemicalenvironment within the second reactor deactivates the single sitecatalyst formulation, or; in parallel mode of operation the chemicalenvironment within stream 12 d deactivates the single site catalystformation.

Referring to the embodiments shown in FIGS. 1 and 2, the amount ofhydrogen added to R2 can vary over a wide range which allows thecontinuous solution process to produce second ethylene interpolymersthat differ greatly in melt index, hereafter I₂ ². This is accomplishedby adjusting the hydrogen flow rate in stream 9. The quantity ofhydrogen added is expressed as the parts-per-million (ppm) of hydrogenin R2 relative to the total mass in reactor R2; hereafter H₂ ^(R2)(ppm). In some cases H₂ ^(R2) (ppm) ranges from about 50 ppm to 0 ppm,in some cases from about 25 ppm to 0 ppm, in other cases from about 10to 0 and in still other cases from about 2 ppm to 0 ppm. The upper limiton I₂ ² may be about 1000 dg/min; in some cases about 750 dg/min; inother cases about 500 dg/min, and; in still other cases about 200dg/min. The lower limit on I₂ ² may be about 0.3 dg/min, in some casesabout 0.4 dg/min, in other cases about 0.5 dg/min, and; in still othercases about 0.6 dg/min.

The upper limit on the weight percent (wt %) of the second ethyleneinterpolymer in the ethylene interpolymer product may be about 85 wt %,in other cases about 80 wt % and in still other cases about 70 wt %. Thelower limit on the wt % of the second ethylene interpolymer in theethylene interpolymer product may be about 30 wt %; in other cases about40 wt % and in still other cases about 50 wt %.

Third Ethylene Interpolymer

Referring to the embodiments shown in FIG. 1 a third ethyleneinterpolymer is not produced in reactor 17 (R3) if catalyst deactivatorA is added upstream of reactor 17 via catalyst deactivator tank 18A. Ifcatalyst deactivator A is not added and optional α-olefin is not addedto reactor 17 either through fresh α-olefin stream 15 or carried overfrom reactor 12 a (R2) in stream 12 c (series mode) or stream 12 d(parallel mode) then the ethylene interpolymer produced in reactor 17 isan ethylene homopolymer. If catalyst deactivator A is not added andoptional α-olefin is present in R3, the following weight ratiodetermines the density of the third ethylene interpolymer:((α-olefin)/(ethylene))^(R3). In the continuous solution polymerizationprocess ((α-olefin)/(ethylene))^(R3) is one of the control parameterused to produce a third ethylene interpolymer with a desired density.The upper limit on ((α-olefin)/(ethylene))^(R3) may be about 3; in othercases about 2 and in still other cases about 1. The lower limit on((α-olefin)/(ethylene))^(R3) may be 0; in other cases about 0.25 and instill other cases about 0.5. Hereafter, the symbol “03” refers to thedensity of the ethylene interpolymer produced in R3. The upper limit onσ³ may be about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; inother cases about 0.955 g/cm³. Depending on the heterogeneous catalystformulations used, the lower limit on σ³ may be about 0.89 g/cm³, insome cases about 0.90 g/cm³, and; in other cases about 0.91 g/cm³.Optionally, a second heterogeneous catalyst formulation may be added toR3. The ranges disclosed in this paragraph also apply to the embodimentsshown in FIG. 2.

Typically, the upper limit on the CDBI₅₀ of the optional third ethyleneinterpolymer (containing an α-olefin) may be about 65%, in other casesabout 60% and in still other cases about 55%. The CDBI₅₀ of an α-olefincontaining optional third ethylene interpolymer will be lower than theCDBI₅₀ of the first ethylene interpolymer produced with the single-sitecatalyst formulation. Typically, the lower limit on the CDBI₅₀ of theoptional third ethylene interpolymer (containing an α-olefin) may beabout 35%, in other cases about 40% and in still other cases about 45%.If an α-olefin is not added to the continuous solution polymerizationprocess the optional third ethylene interpolymer is an ethylenehomopolymer. In the case of an ethylene homopolymer the upper limit onthe CDBI₅₀ may be about 98%, in other cases about 96% and in still othercases about 95%, and; the lower limit on the CDBI₅₀ may be about 88%, inother cases about 89% and in still other cases about 90%. Typically, theCDBI₅₀ of the first ethylene interpolymer is higher than the CDBI₅₀ ofthe third ethylene interpolymer and second ethylene interpolymer.

The upper limit on the M_(w)/M_(n) of the optional third ethyleneinterpolymer may be about 5.0, in other cases about 4.8 and in stillother cases about 4.5. The lower limit on the M_(w)/M_(n) of theoptional third ethylene interpolymer may be about 2.2, in other casesabout 2.4 and in still other cases about 2.6. The M_(w)/M_(n) of theoptional third ethylene interpolymer is higher than the M_(w)/M_(n) ofthe first ethylene interpolymer. When blended together, the second andthird ethylene interpolymer have a fourth M_(w)/M_(n) which is notbroader than the M_(w)/M_(n) of the second ethylene interpolymer.

The catalyst residues in the optional third ethylene interpolymerreflect the chemical composition of the heterogeneous catalystformulation(s) used, i.e. the first and optionally a secondheterogeneous catalyst formulation. The chemical compositions of thefirst and second heterogeneous catalyst formulations may be the same ordifferent; for example, a first component (vii) and a second component(vii) may be used to synthesize the first and second heterogeneouscatalyst formulation. As recited above, “metal B” refers to the metalthat originates from the first component (vii). Hereafter, “metal C”refers to the metal that originates from the second component (vii).Metal B and optional metal C may be the same, or different. Non-limitingexamples of metal B and metal C include metals selected from Group 4through Group 8 of the Periodic Table, or mixtures of metals selectedfrom Group 4 through Group 8. The upper limit on the ppm of (metalB+metal C) in the optional third ethylene interpolymer may be about 12ppm, in other cases about 10 ppm and in still other cases about 8 ppm.The lower limit on the ppm of (metal B+metal C) in the optional thirdethylene interpolymer may be about 2 ppm, in other cases about 3 ppm andin still other cases about 4 ppm.

Referring to the embodiments shown in FIGS. 1 and 2, optional hydrogenmay be added to the tubular reactor (R3) via stream 16. The amount ofhydrogen added to R3 may vary over a wide range. Adjusting the amount ofhydrogen in R3, hereafter H₂ ^(R3) (ppm), allows the continuous solutionprocess to produce optional third ethylene interpolymers that differwidely in melt index, hereafter I₂ ³. The amount of optional hydrogenadded to R3 ranges from about 50 ppm to 0 ppm, in some cases from about25 ppm to 0 ppm, in other cases from about 10 to 0 and in still othercases from about 2 ppm to 0 ppm. The upper limit on I₂ ³ may be about2000 dg/min; in some cases about 1500 dg/min; in other cases about 1000dg/min, and; in still other cases about 500 dg/min. The lower limit onI₂ ³ may be about 0.5 dg/min, in some cases about 0.6 dg/min, in othercases about 0.7 dg/min, and; in still other cases about 0.8 dg/min.

The upper limit on the weight percent (wt %) of the optional thirdethylene interpolymer in the ethylene interpolymer product may be about30 wt %, in other cases about 25 wt % and in still other cases about 20wt %. The lower limit on the wt % of the optional third ethyleneinterpolymer in the ethylene interpolymer product may be 0 wt %; inother cases about 5 wt % and in still other cases about 10 wt %.

Ethylene Interpolymer Product

The upper limit on the density of the ethylene interpolymer product maybe about 0.975 g/cm³; in some cases about 0.965 g/cm³ and; in othercases about 0.955 g/cm³. The lower limit on the density of the ethyleneinterpolymer product may be about 0.869 g/cm³, in some cases about 0.879g/cm³, and; in other cases about 0.889 g/cm³.

The upper limit on the CDBI₅₀ of the ethylene interpolymer product maybe about 97%, in other cases about 90% and in still other cases about85%. An ethylene interpolymer product with a CDBI₅₀ of 97% may result ifan α-olefin is not added to the continuous solution polymerizationprocess; in this case, the ethylene interpolymer product is an ethylenehomopolymer. The lower limit on the CDBI₅₀ of an ethylene interpolymermay be about 20%, in other cases about 40% and in still other casesabout 60%.

The upper limit on the M_(w)/M_(n) of the ethylene interpolymer productmay be about 25, in other cases about 15 and in still other cases about9. The lower limit on the M_(w)/M_(n) of the ethylene interpolymerproduct may be 2.0, in other cases about 2.2 and in still other casesabout 2.4.

The catalyst residues in the ethylene interpolymer product reflect thechemical compositions of: the single-site catalyst formulation employedin R1; the first heterogeneous catalyst formulation employed in R2, and;optionally the first or optionally the first and second heterogeneouscatalyst formulation employed in R3. In this disclosure, catalystresidues were quantified by measuring the parts per million of catalyticmetal in the ethylene interpolymer products. In addition, the elementalquantities (ppm) of magnesium, chlorine and aluminum were quantified.Catalytic metals originate from two or optionally three sources,specifically: 1) “metal A” that originates from component (i) that wasused to form the single-site catalyst formulation; (2) “metal B” thatoriginates from the first component (vii) that was used to form thefirst heterogeneous catalyst formulation, and; (3) optionally “metal C”that originates from the second component (vii) that was used to formthe optional second heterogeneous catalyst formulation. Metals A, B andC may be the same or different. In this disclosure the term “totalcatalytic metal” is equivalent to the sum of catalytic metals A+B+C.Further, in this disclosure the terms “first total catalytic metal” and“second total catalyst metal” are used to differentiate between theamount of catalytic metal in the first and second ethylene interpolymer.

The upper limit on the ppm of metal A in the ethylene interpolymerproduct may be about 0.6 ppm, in other cases about 0.5 ppm and in stillother cases about 0.4 ppm. The lower limit on the ppm of metal A in theethylene interpolymer product may be about 0.001 ppm, in other casesabout 0.01 ppm and in still other cases about 0.03 ppm. The upper limiton the ppm of (metal B+metal C) in the ethylene interpolymer product maybe about 11 ppm, in other cases about 9 ppm and in still other casesabout 7 ppm. The lower limit on the ppm of (metal B+metal C) in theethylene interpolymer product may be about 2 ppm, in other cases about 3ppm and in still other cases about 4 ppm.

In some embodiments, ethylene interpolymers may be produced where thecatalytic metals (metals A, B and C) are the same metal; a non-limitingexample would be titanium. In such embodiments, the ppm of (metalB+metal C) in the ethylene interpolymer product is calculated usingequation (VII):ppm^((B+C))=((ppm^((A+B+C))−(f ^(A)×ppm^(A)))/(1−f ^(A))  (VII)

where: ppm^((B+C)) is the calculated ppm of (metal B+metal C) in theethylene interpolymer product; ppm^((A+B+C)) is the total ppm ofcatalyst residue in the ethylene interpolymer product as measuredexperimentally, i.e. (metal A ppm+metal B ppm+metal C ppm); f^(A)represents the weight fraction of the first ethylene interpolymer in theethylene interpolymer product, f^(A) may vary from about 0.15 to about0.6, and; ppm^(A) represents the ppm of metal A in the first ethyleneinterpolymer. In equation (VII) ppm^(A) is assumed to be 0.35 ppm.

Embodiments of the ethylene interpolymer products disclosed herein havelower catalyst residues relative to the polyethylene polymers describedin U.S. Pat. No. 6,277,931. Higher catalyst residues in U.S. Pat. No.6,277,931 increase the complexity of the continuous solutionpolymerization process; an example of increased complexity includesadditional purification steps to remove catalyst residues from thepolymer. In contrast, in the present disclosure, catalyst residues arenot removed. In this disclosure, the upper limit on the “total catalyticmetal”, i.e., the total ppm of (metal A ppm+metal B ppm+optional metal Cppm) in the ethylene interpolymer product may be about 11 ppm, in othercases about 9 ppm and in still other cases about 7, and; the lower limiton the total ppm of catalyst residuals (metal A+metal B+optional metalC) in the ethylene interpolymer product may be about 2 ppm, in othercases about 3 ppm and in still other cases about 4 ppm.

The upper limit on melt index of the ethylene interpolymer product maybe about 500 dg/min, in some cases about 400 dg/min; in other casesabout 300 dg/min, and; in still other cases about 200 dg/min. The lowerlimit on the melt index of the ethylene interpolymer product may beabout 0.3 dg/min, in some cases about 0.4 dg/min; in other cases about0.5 dg/min, and; in still other cases about 0.6 dg/min.

A computer generated ethylene interpolymer product is illustrated inTable 3; this simulations was based on fundamental kinetic models (withkinetic constants specific for each catalyst formulation) as well asfeed and reactor conditions. The simulation was based on theconfiguration of the solution pilot plant described below; which wasused to produce the examples of ethylene interpolymer products disclosedherein. Simulated Example 13 was synthesized using a single-sitecatalyst formulation (PIC-1) in R1 and an in-line Ziegler-Natta catalystformulation in R2 and R3. Table 7 discloses a non-limiting example ofthe density, melt index and molecular weights of the first, second andthird ethylene interpolymers produced in the three reactors (R1, R2 andR3); these three interpolymers are combined to produce Simulated Example13 (the ethylene polymer product). As shown in Table 7, the SimulatedExample 13 product has a density of 0.9169 g/cm³, a melt index of 1.0dg/min, a branch frequency of 12.1 (the number of C₆-branches per 1000carbon atoms (1-octene comonomer)) and a M_(w)/M_(n) of 3.11. SimulatedExample 13 comprises: a first, second and third ethylene interpolymerhaving a first, second and third melt index of 0.31 dg/min, 1.92 dg/minand 4.7 dg/min, respectively; a first, second and third density of0.9087 g/cm³, 0.9206 g/cm³ and 0.9154 g/cm³, respectively; a first,second and third M_(w)/M_(n) of 2.03 M_(w)/M_(n), 3.29 M_(w)/M_(n) and3.28 M_(w)/M_(n), respectively, and; a first, second and third CDBI₅₀ of90 to 95%, 55 to 60% and 45 to 55%, respectively. The simulatedproduction rate of Simulated Example 13 was 90.9 kg/hr and the R3 exittemperature was 217.1° C.

Ethylene Interpolymer Product Examples

Tables 1A through 1C summarize solution process conditions used toproduce ethylene interpolymer products Example 6 and 7, as well asComparative Example 3; the target melt index and density targets ofthese samples were 0.60 dg/min and 0.915 g/cm³. Example 6 and 7 wereproduced using a single-site catalyst in R1 and an in-line Ziegler-Nattacatalyst in R2. In contrast, Comparative Example 3 was produced using asingle-site catalyst in both reactors R1 and R2. Table 1A-1C show higherproduction rates (kg/h) for Examples 6 and 7, relative to ComparativeExample 3. In Examples 6 and 7 ethylene interpolymer products wereproduced at 85.2 and 94 kg/h, respectively; 13% and 24% higher,respectively, relative to Comparative Example 3 at 75.6 kg/h.

Examples 6 and 7 are two non-limiting embodiments of this disclosure;selected physical properties of Examples 6 and 7 are summarized in Table2.

Example 6 is an ethylene interpolymer product that has a Dilution Index(Y_(d)) of 4.69; a Dimensionless Modulus (X_(d)) of −0.08; 5.2 ppm oftotal catalytic metal (titanium), and; 0.038 terminal vinyls/100 carbonatoms. The Dilution Index (Y_(d)) and Dimensionless Modulus (X_(d)) arefully described in the next section of this disclosure.

Dilution Index (Y_(d)) of Ethylene Interpolymer Products

In FIG. 3 the Dilution Index (Y_(d), having dimensions of ° (degrees))and Dimensionless Modulus (X_(d)) are plotted for several embodiments ofthe ethylene interpolymer products disclosed herein (the solid symbols),as well as comparative ethylene interpolymer products, i.e., ComparativeA, D, E and S. Further, FIG. 3 defines the following three quadrants:

-   -   Type I: Y_(d)>0 and X_(d)<0;    -   Type II: Y_(d)>0 and X_(d)>0, and;    -   Type II: Y_(d)<0 and X_(d)>0.

The data plotted in FIG. 3 is also tabulated in Table 4. In FIG. 3,Comparative S (open triangle) was used as the rheological reference inthe Dilution Index test protocol. Comparative S is an ethyleneinterpolymer product comprising an ethylene interpolymer synthesizedusing an in-line Ziegler-Natta catalyst in one solution reactor, i.e.SCLAIR® FP120-C which is an ethylene/1-octene interpolymer availablefrom NOVA Chemicals Company (Calgary, Alberta, Canada). Comparatives Dand E (open diamonds, Y_(d)<0, X_(d)>0) are ethylene interpolymerproducts comprising a first ethylene interpolymer synthesized using asingle-site catalyst formation and a second ethylene interpolymersynthesized using a batch Ziegler-Natta catalyst formulation employing adual reactor solution process, i.e. Elite® 5100G and Elite® 5400G,respectively, both ethylene/1-octene interpolymers available from TheDow Chemical Company (Midland, Mich., USA). Comparative A (open square,Y_(d)>0 and X_(d)<0) was an ethylene interpolymer product comprising afirst and second ethylene interpolymer synthesized using a single-sitecatalyst formation in a dual reactor solution process, i.e., SURPASS®FPs117-C which is an ethylene/1-octene interpolymer available from NOVAChemicals Company (Calgary, Alberta, Canada).

The following defines the Dilution Index (Y_(d)) and DimensionlessModulus (X_(d)). In addition to having molecular weights, molecularweight distributions and branching structures, blends of ethyleneinterpolymers may exhibit a hierarchical structure in the melt phase. Inother words, the ethylene interpolymer components may be, or may not be,homogeneous down to the molecular level depending on interpolymermiscibility and the physical history of the blend. Such hierarchicalphysical structure in the melt is expected to have a strong impact onflow and hence on processing and converting; as well as the end-useproperties of manufactured articles. The nature of this hierarchicalphysical structure between interpolymers can be characterized.

The hierarchical physical structure of ethylene interpolymers can becharacterized using melt rheology. A convenient method can be based onthe small amplitude frequency sweep tests. Such rheology results areexpressed as the phase angle δ as a function of complex modulus G*,referred to as van Gurp-Palmen plots (as described in M. Van Gurp, J.Palmen, Rheol. Bull. (1998) 67(1): 5-8, and; Dealy J, Plazek D. Rheol.Bull. (2009) 78(2): 16-31). For a typical ethylene interpolymer, thephase angle S increases toward its upper bound of 90° with G* becomingsufficiently low. A typical VGP plot is shown in FIG. 4. The VGP plotsare a signature of resin architecture. The rise of δ toward 90° ismonotonic for an ideally linear, monodisperse interpolymer. The S(G*)for a branched interpolymer or a blend containing a branchedinterpolymer may show an inflection point that reflects the topology ofthe branched interpolymer (see S. Trinkle, P. Walter, C. Friedrich,Rheo. Acta (2002) 41: 103-113). The deviation of the phase angle δ fromthe monotonic rise may indicate a deviation from the ideal linearinterpolymer either due to presence of long chain branching if theinflection point is low (e.g., δ≤20°) or a blend containing at least twointerpolymers having dissimilar branching structure if the inflectionpoint is high (e.g., δ≥70θ).

For commercially available linear low density polyethylenes, inflectionpoints are not observed; with the exception of some commercialpolyethylenes that contain a small amount of long chain branching (LCB).To use the VGP plots regardless of presence of LCB, an alternative is touse the point where the frequency ω_(c) is two decades below thecross-over frequency ω_(c), i.e., ω_(c)=0.01ω_(x). The cross-over pointis taken as the reference as it is known to be a characteristic pointthat correlates with MI, density and other specifications of an ethyleneinterpolymer. The cross-over modulus is related to the plateau modulusfor a given molecular weight distribution (see S. Wu. J Polym Sci, PolymPhys Ed (1989) 27:723; M. R. Nobile, F. Cocchini. Rheol Acta (2001)40:111). The two decade shift in phase angle δ is to find the comparablepoints where the individual viscoelastic responses of constituents couldbe detected; to be more clear, this two decade shift is shown in FIG. 5.The complex modulus G_(c)* for this point is normalized to thecross-over modulus, G_(x)*/(√{square root over (2)}), as (√{square rootover (2)})G_(c)*/G_(x)*, to minimize the variation due to overallmolecular weight, molecular weight distribution and the short chainbranching. As a result, the coordinates on VGP plots for this lowfrequency point at ω_(c)=0.01ω_(x), namely (√{square root over(2)})G_(c)*/G_(x)* and δ_(c), characterize the contribution due toblending. Similar to the inflection points, the closer the ((√{squareroot over (2)})G_(c)*/G_(x)*, δ_(c)) point is toward the 90° upperbound, the more the blend behaves as if it were an ideal singlecomponent.

As an alternative way to avoid interference due to the molecular weight,molecular weight distribution and the short branching of the ethyleneδ_(c) interpolymer ingredients, the coordinates (G_(c)*, δ_(c)) arecompared to a reference sample of interest to form the following twoparameters:

“Dilution Index (Y_(d))”Y _(d)=δ_(c)−(C ₀ −C ₁ e ^(C) ² ^(ln G) ^(c) ^(*))

“Dimensionless Modulus (X_(d))”X _(d) =G _(0.01ω) _(c) */G _(r)*

The constants C₀, C₁, and C₂ are determined by fitting the VGP dataδ(G*) of the reference sample to the following equation:δ=C ₀ −C ₁ e ^(C) ² ^(ln G*)G_(r)* is the complex modulus of this reference sample at itsδ_(c)=δ(0.01ω_(x)). When an ethylene interpolymer, synthesized with anin-line Ziegler-Natta catalyst employing one solution reactor, having adensity of 0.920 g/cm³ and a melt index (MI or I₂) of 1.0 dg/min istaken as a reference sample, the constants are:

C₀=93.43°

C₁=1.316°

C₂=0.2945

G_(r)*=9432 Pa.

The values of these constants can be different if the rheology testprotocol differs from that specified herein.

These regrouped coordinates (X_(d), Y_(d)) from (G_(c)*, δ_(c)) allowscomparison between ethylene interpolymer products disclosed herein withComparative examples. The Dilution Index (Y_(d)) reflects whether theblend behaves like a simple blend of linear ethylene interpolymers(lacking hierarchical structure in the melt) or shows a distinctiveresponse that reflects a hierarchical physical structure within themelt. The lower the Y_(d), the more the sample shows separate responsesfrom the ethylene interpolymers that comprise the blend; the higher theY_(d) the more the sample behaves like a single component, or singleethylene interpolymer.

Returning to FIG. 3: Type I (upper left quadrant) ethylene interpolymerproducts of this disclosure (solid symbols) have Y_(d)>0; in contrast,Type III (lower right quadrant) comparative ethylene interpolymers,Comparative D and E have Y_(d)<0. In the case of Type I ethyleneinterpolymer products (solid circles), the first ethylene interpolymer(single-site catalyst) and the second ethylene interpolymer (in-lineZiegler Natta catalyst) behave as a simple blend of two ethyleneinterpolymers and a hierarchical structure within the melt does notexist. However, in the case of Comparatives D and E (open diamonds), themelt comprising a first ethylene interpolymer (single-site catalyst) anda second ethylene interpolymer (batch Ziegler Natta catalyst) possessesa hierarchical structure.

The ethylene interpolymer products of this disclosure fall into one oftwo quadrants: Type I with X_(d)<0, or; Type II with X_(d)>0. TheDimensionless Modulus (X_(d)), reflects differences (relative to thereference sample) that are related to the overall molecular weight,molecular weight distribution (M_(w)/M_(n)) and short chain branching.Not wishing to be bound by theory, conceptually, the DimensionlessModulus (X_(d)) may be considered to be related to the M_(w)/M_(n) andthe radius of gyration (<R_(g)>2) of the ethylene interpolymer in themelt; conceptually, increasing X_(d) has similar effects as increasingM_(w)/M_(n) and/or <R_(g)>2, without the risk of including lowermolecular weight fraction and sacrificing certain related properties.

Relative to Comparative A (recall that Comparative A comprises a firstand second ethylene interpolymer synthesized with a single-sitecatalyst) the solution process disclosed herein enables the manufactureof ethylene interpolymer products having higher X_(d). Not wishing to bebound by theory, as X_(d) increases the macromolecular coils of highermolecular weight fraction are more expanded (conceptually higher<R_(g)>2) and upon crystallization the probability of tie chainformation is increased resulting in higher toughness properties; thepolyethylene art is replete with disclosures that correlate highertoughness (higher dart impact in film applications and improved ESCRand/or PENT in molding applications) with an increasing probability oftie chain formation.

In the Dilution Index testing protocol, the upper limit on Y_(d) may beabout 20, in some cases about 15 and is other cases about 13. The lowerlimit on Y_(d) may be about −30, in some cases −25, in other cases −20and in still other cases −15.

In the Dilution Index testing protocol, the upper limit on X_(d) is 1.0,in some cases about 0.95 and in other cases about 0.9. The lower limiton X_(d) is −2, in some cases −1.5 and in still other cases −1.0.

Terminal Vinyl Unsaturation of Ethylene Interpolymer Products

The ethylene interpolymer products of this disclosure are furthercharacterized by a terminal vinyl unsaturation greater than or equal to0.03 terminal vinyl groups per 100 carbon atoms (≥0.03 terminalvinyls/100 C); as determine via Fourier Transform Infrared (FTIR)spectroscopy according to ASTM ASTM D3124-98 and ASTM D6248-98.

FIG. 6 compares the terminal vinyl/100 C content of the ethyleneinterpolymers of this disclosure with several Comparatives. The datashown in FIG. 6 is also tabulated in Tables 5A and 5B. All of thecomparatives in FIG. 6 and Tables 5A and 5B are Elite® productsavailable from The Dow Chemical Company (Midland, Mich., USA); Eliteproducts are ethylene interpolymers produced in a dual reactor solutionprocess and comprise an interpolymer synthesized using a single-sitecatalyst and an interpolymer synthesized using a batch Ziegler-Nattacatalyst: Comparative B is Elite 5401G; Comparative C is Elite 5400G;Comparative E and E2 are Elite 5500G; Comparative G is Elite 5960;Comparative H and H2 are Elite 5100G; Comparative I is Elite 5940G, and;Comparative J is Elite 5230G.

As shown in FIG. 6 the average terminal vinyl content in the ethyleneinterpolymer of this disclosure was 0.045 terminal vinyls/100 C; incontrast, the average terminal vinyl content in the Comparative sampleswas 0.023 terminal vinyls/100 C. Statistically, at the 99.999%confidence level, the ethylene interpolymers of this disclosure aresignificantly different from the Comparatives; i.e. a t-Test assumingequal variances shows that the means of the two populations (0.045 and0.023 terminal vinyls/100 C) are significantly different at the 99.999%confidence level (t(obs)=12.891>3.510 t(crit two tail); orp-value=4.84×10⁻¹⁷<0.001 α (99.999% confidence)).

Catalyst Residues (Total Catalytic Metal)

The ethylene interpolymer products of this disclosure are furthercharacterized by having ≥3 parts per million (ppm) of total catalyticmetal (Ti); where the quantity of catalytic metal was determined byNeutron Activation Analysis (N.A.A.) as specified herein.

FIG. 7 compares the total catalytic metal content of the disclosedethylene interpolymers with several Comparatives; FIG. 7 data is alsotabulated in Tables 6A and 6B. All of the comparatives in FIG. 7 andTables 6A and 6B are Elite® products available from The Dow ChemicalCompany (Midland, Mich., USA), for additional detail see the sectionabove.

As shown in FIG. 7 the average total catalytic metal content in theethylene interpolymers of this disclosure was 7.02 ppm of titanium; incontrast, the average total catalytic metal content in the Comparativesamples was 1.63 ppm of titanium. Statistically, at the 99.999%confidence level, the ethylene interpolymers of this disclosure aresignificantly different from the Comparatives, i.e., a t-Test assumingequal variances shows that the means of the two populations (7.02 and1.63 ppm titanium) are significantly different at the 99.999% confidencelevel, i.e. (t(obs)=12.71>3.520 t(crit two tail); orp-value=1.69×10⁻¹⁶<0.001 α (99.999% confidence)).

Flexible Manufactured Articles

Ethylene interpolymer products disclosed herein may be converted into awide variety of flexible manufactured articles. Non-limiting examplesinclude monolayer or multilayer films. Such films are well known tothose of ordinary sill in the art. Non-limiting examples of processes toprepare such films include blown film and cast film processes.

Depending on the end-use application, the disclosed ethyleneinterpolymer products may be converted into films that span a wide rangeof thicknesses. Non-limiting examples include, food packaging filmswhere thicknesses may range from about 0.5 mil (13 μm) to about 4 mil(102 μm), and; in heavy duty sack applications film thickness may rangefrom about 2 mil (51 μm) to about 10 mil (254 μm).

The disclosed ethylene interpolymer products may be used in monolayerfilms; where the monolayer comprises one or more of the disclosedethylene interpolymer products and optionally additional thermoplastics;non-limiting examples of thermoplastics include ethylene polymers andpropylene polymers. The lower limit on the weight percent of theethylene interpolymer product in a monolayer film may be about 3 wt %,in other cases about 10 wt % and in still other cases about 30 wt %. Theupper limit on the weight percent of the ethylene interpolymer productin the monolayer film may be 100 wt %, in other cases about 90 wt % andin still other cases about 70 wt %.

The ethylene interpolymer products disclosed herein may also be used inone or more layers of a multilayer film; non-limiting examples ofmultilayer films include three, five, seven, nine, eleven or morelayers. The thickness of a specific layer (containing one or moreethylene interpolymer product(s)) within the multilayer film may beabout 5%, in other cases about 15% and in still other cases about 30% ofthe total multilayer film thickness. In other embodiments, the thicknessof a specific layer (containing one or more ethylene interpolymerproduct(s)) within the multilayer film may be about 95%, in other casesabout 80% and in still other cases about 65% of the total multilayerfilm thickness. Each individual layer of a multilayer film may containmore than one ethylene interpolymer product and/or additionalthermoplastics.

Additional embodiments include laminations and coatings, wherein mono ormultilayer films containing the disclosed ethylene interpolymer productsare extrusion laminated or adhesively laminated or extrusion coated. Inextrusion lamination or adhesive lamination, two or more substrates arebonded together with a thermoplastic or an adhesive, respectively. Inextrusion coating, a thermoplastic is applied to the surface of asubstrate. These processes are well known to those of ordinaryexperience in the art.

The ethylene interpolymer products disclosed herein can be used in awide range of manufactured articles comprising one or more films(monolayer or multilayer). Non-limiting examples of such manufacturedarticles include: food packaging films (fresh and frozen foods, liquidsand granular foods), stand-up pouches, retortable packaging andbag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.)and modified atmosphere packaging; light and heavy duty shrink films andwraps, collation shrink film, pallet shrink film, shrink bags, shrinkbundling and shrink shrouds; light and heavy duty stretch films, handstretch wrap, machine stretch wrap and stretch hood films; high clarityfilms; heavy-duty sacks; household wrap, overwrap films and sandwichbags; industrial and institutional films, trash bags, can liners,magazine overwrap, newspaper bags, mail bags, sacks and envelopes,bubble wrap, carpet film, furniture bags, garment bags, coin bags, autopanel films; medical applications such as gowns, draping and surgicalgarb; construction films and sheeting, asphalt films, insulation bags,masking film, landscaping film and bags; geomembrane liners formunicipal waste disposal and mining applications; batch inclusion bags;agricultural films, mulch film and green house films; in-storepackaging, self-service bags, boutique bags, grocery bags, carry-outsacks and t-shirt bags; oriented films, machine direction and biaxiallyoriented films and functional film layers in oriented polypropylene(OPP) films, e.g., sealant and/or toughness layers. Additionalmanufactured articles comprising one or more films containing at leastone ethylene interpolymer product include laminates and/or multilayerfilms; sealants and tie layers in multilayer films and composites;laminations with paper; aluminum foil laminates or laminates containingvacuum deposited aluminum; polyamide laminates; polyester laminates;extrusion coated laminates, and; hot-melt adhesive formulations. Themanufactured articles summarized in this paragraph contain at least onefilm (monolayer or multilayer) comprising at least one embodiment of thedisclosed ethylene interpolymer products.

The disclosed ethylene interpolymer products have performance attributesthat are advantageous in many flexible applications. The performanceattribute(s) required depends on how the film will be used, i.e., thespecific film application the film is employed in. The disclosedethylene interpolymer products have a desirable balance of properties.Elaborating, relative to competitive polyethylenes of similar densityand melt index, the disclosed ethylene interpolymers have one or moreof: higher stiffness (e.g. tensile and/or flex modulus); highertoughness properties (e.g., impact and puncture); higher heat deflectiontemperatures; higher Vicat softening point; improved color (WI and YI);higher melt strength, and; improved heat sealing properties (e.g., heatsealing and hot tack). The recited performance attributes, in theprevious sentence, are not to be construed as limiting. Further, thepolymerization process and catalyst formulations disclosed herein allowthe production of ethylene interpolymer products that can be convertedinto flexible manufactured articles that have a unique balance ofphysical properties (i.e., a several end-use properties can be balanced(as desired) in a multidimensional optimization); relative tocomparative polyethylenes of comparable density and melt index.

Rigid Manufactured Articles

The disclosed ethylene interpolymer products may be converted into awide variety of rigid manufactured articles, non-limiting examplesinclude: deli containers, margarine tubs, drink cups and produce trays,bottle cap liners and bottle caps (for carbonated or non-carbonatedfluids), closures (including closures with living hinge functionality),household and industrial containers, cups, bottles, pails, crates,tanks, drums, bumpers, lids, industrial bulk containers, industrialvessels, material handling containers, toys, bins, playground equipment,recreational equipment, boats, marine equipment, safety equipment(helmets), wire and cable applications such as power cables,communication cables and conduits, flexible tubing and hoses, pipeapplications including both pressure pipe and non-pressure pipe markets(e.g., natural gas distribution, water mains, interior plumbing, stormsewer, sanitary sewer, corrugated pipes and conduit), foamed articlesmanufactured from foamed sheet or bun foam, military packaging(equipment and ready meals), personal care packaging, diapers andsanitary products, cosmetic/pharmaceutical/medical packaging, truck bedliners, pallets and automotive dunnage.

The rigid manufactured articles summarized above contain one or more ofthe disclosed ethylene interpolymer products or a blend of at least oneethylene interpolymer product with at least one other thermoplastic.Further, the rigid manufactured articles summarized above may bemultilayer, comprising at least one layer comprising one or moreethylene interpolymer product or a blend of at least one ethyleneinterpolymer product with at least one other thermoplastic. Such rigidmanufactured articles may be fabricated using the following non-limitingprocesses: injection molding, compression molding, blow molding,rotomolding, profile extrusion, pipe extrusion, sheet thermoforming andfoaming processes employing chemical or physical blowing agents.

The disclosed ethylene interpolymer products have performance attributesthat are advantageous in many rigid applications. The specificperformance attribute required depends on how the article will be used,i.e., the specific application. The disclosed ethylene interpolymerproducts have a desirable balance of properties. Elaborating, relativeto competitive polyethylenes of similar density and melt index, thedisclosed ethylene interpolymers have one or more of: higher stiffness(e.g., flexural modulus); higher toughness properties (e.g., ESCR, PENT,IZOD impact, arm impact, Dynatup impact or Charpy impact resistance);higher melt strength, higher heat deflection temperature; higher Vicatsoftening temperatures, improved color (WI and YI), and; fastercrystallization rates. The recited performance attributes, in theprevious sentence, are not to be construed as limiting. Further, thepolymerization process and catalyst formulations disclosed herein allowthe production of ethylene interpolymer products that can be convertedinto rigid manufactured articles that have a unique balance of physicalproperties (i.e., several end-use properties can be balanced (asdesired) through multidimensional optimization); relative to comparativepolyethylenes of comparable density and melt index.

Additives and Adjuvants

The disclosed ethylene interpolymer products used to manufacturearticles described above may optionally include, depending on itsintended use, additives and adjuvants. Non-limiting examples ofadditives and adjuvants include, anti-blocking agents, antioxidants,heat stabilizers, slip agents, processing aids, anti-static additives,colorants, dyes, filler materials, light stabilizers, heat stabilizers,light absorbers, lubricants, pigments, plasticizers, nucleating agentsand combinations thereof. Non-limiting examples of suitable primaryantioxidants include Irganox 1010 [CAS Reg. No. 6683-19-8] and Irganox1076 [CAS Reg. No. 2082-79-3]; both available from BASF Corporation,Florham Park, N.J., U.S.A. Non-limiting examples of suitable secondaryantioxidants include Irgafos 168 [CAS Reg. No. 31570-04-4], availablefrom BASF Corporation, Florham Park, N.J., U.S.A.; Weston 705 [CAS Reg.No. 939402-02-5], available from Addivant, Danbury Conn., U.S.A. and;Doverphos Igp-11 [CAS Reg. No. 1227937-46-3] available form DoverChemical Corporation, Dover Ohio, U.S.A.

Testing Methods

Prior to testing, each specimen was conditioned for at least 24 hours at23±2C and 50±10% relative humidity and subsequent testing was conductedat 23±2° C. and 50±10% relative humidity. Herein, the term “ASTMconditions” refers to a laboratory that is maintained at 23±2C and50±10% relative humidity; and specimens to be tested were conditionedfor at least 24 hours in this laboratory prior to testing. ASTM refersto the American Society for Testing and Materials.

Density

Ethylene interpolymer product densities were determined using ASTMD792-13 (Nov. 1, 2013).

Melt Index

Ethylene interpolymer product melt index was determined using ASTM D1238(Aug. 1, 2013). Melt indexes, I₂, I₆, I₁₀ and I₂₁ were measured at 190°C., using weights of 2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively.Melt index is commonly report with units of g/10 minute or dg/minute;these units are equivalent and the latter was used in this disclosure.Herein, the term “stress exponent” or its acronym “S.Ex.”, is defined bythe following relationship:S.Ex.=log(I ₆ /I ₂)/log(6480/2160)

wherein I₆ and I₂ are the melt flow rates measured at 190° C. using 6.48kg and 2.16 kg loads, respectively. In this disclosure, melt index wasexpressed using the units of g/10 minute or g/10 min or dg/minute ordg/min; these units are equivalent.

Gel Permeation Chromatography (GPC)

Ethylene interpolymer product molecular weights, M_(n), M_(w) and M_(z),as well the as the polydispersity (M_(w)/M_(n)), were determined usingASTM D6474-12 (Dec. 15, 2012). This method illuminates the molecularweight distributions of ethylene interpolymer products by hightemperature gel permeation chromatography (GPC). The method usescommercially available polystyrene standards to calibrate the GPC.

Unsaturation Content

The quantity of unsaturated groups, i.e. double bonds, in an ethyleneinterpolymer product was determined according to ASTM D3124-98(vinylidene unsaturation, published March 2011) and ASTM D6248-98 (vinyland trans unsaturation, published July 2012). An ethylene interpolymersample was: a) first subjected to a carbon disulfide extraction toremove additives that may interfere with the analysis; b) the sample(pellet, film or granular form) was pressed into a plaque of uniformthickness (0.5 mm), and; c) the plaque was analyzed by FTIR.

Comonomer Content

The quantity of comonomer in an ethylene interpolymer product wasdetermined by FTIR (Fourier Transform Infrared spectroscopy) accordingto ASTM D6645-01 (published January 2010).

Composition Distribution Branching Index (CDBI)

The “Composition Distribution Branching Index” or “CDBI” of thedisclosed Examples and Comparative Examples were determined using acrystal-TREF unit commercially available form Polymer ChAR (Valencia,Spain). The acronym “TREF” refers to Temperature Rising ElutionFractionation. A sample of ethylene interpolymer product (80 to 100 mg)was placed in the reactor of the Polymer ChAR crystal-TREF unit, thereactor was filled with 35 ml of 1,2,4-trichlorobenzene (TCB), heated to150° C. and held at this temperature for 2 hours to dissolve the sample.An aliquot of the TCB solution (1.5 mL) was then loaded into the PolymerChAR TREF column filled with stainless steel beads and the column wasequilibrated for 45 minutes at 110° C. The ethylene interpolymer productwas then crystallized from the TCB solution, in the TREF column, byslowly cooling the column from 110° C. to 30° C. using a cooling rate of0.09° C. per minute. The TREF column was then equilibrated at 30° C. for30 minutes. The crystallized ethylene interpolymer product was theneluted from the TREF column by passing pure TCB solvent through thecolumn at a flow rate of 0.75 mL/minute as the temperature of the columnwas slowly increased from 30° C. to 120° C. using a heating rate of0.25° C. per minute. Using Polymer ChAR software a TREF distributioncurve was generated as the ethylene interpolymer product was eluted fromthe TREF column, i.e., a TREF distribution curve is a plot of thequantity (or intensity) of ethylene interpolymer eluting from the columnas a function of TREF elution temperature. A CDBI₅₀ was calculated fromthe TREF distribution curve for each ethylene interpolymer productanalyzed. The “CDBI₅₀” is defined as the percent of ethyleneinterpolymer whose composition is within 50% of the median comonomercomposition (25% on each side of the median comonomer composition); itis calculated from the TREF composition distribution curve and thenormalized cumulative integral of the TREF composition distributioncurve. Those skilled in the art will understand that a calibration curveis required to convert a TREF elution temperature to comonomer content,i.e. the amount of comonomer in the ethylene interpolymer fraction thatelutes at a specific temperature. The generation of such calibrationcurves are described in the prior art, e.g., Wild, et al., J. Polym.Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455: hereby fullyincorporated by reference.

Neutron Activation Analysis (NAA)

Neutron Activation Analysis, hereafter NAA, was used to determinecatalyst residues in ethylene interpolymers and was performed asfollows. A radiation vial (composed of ultrapure polyethylene, 7 mLinternal volume) was filled with an ethylene interpolymer product sampleand the sample weight was recorded. Using a pneumatic transfer systemthe sample was placed inside a SLOWPOKE™ nuclear reactor (Atomic Energyof Canada Limited, Ottawa, Ontario, Canada) and irradiated for 30 to 600seconds for short half-life elements (e.g., Ti, V, Al, Mg, and Cl) or 3to 5 hours for long half-life elements (e.g., Zr, Hf, Cr, Fe and Ni).The average thermal neutron flux within the reactor was 5×10¹¹/cm²/s.After irradiation, samples were withdrawn from the reactor and aged,allowing the radioactivity to decay; short half-life elements were agedfor 300 seconds or long half-life elements were aged for several days.After aging, the gamma-ray spectrum of the sample was recorded using agermanium semiconductor gamma-ray detector (Ortec model GEM55185,Advanced Measurement Technology Inc., Oak Ridge, Tenn., USA) and amultichannel analyzer (Ortec model DSPEC Pro). The amount of eachelement in the sample was calculated from the gamma-ray spectrum andrecorded in parts per million relative to the total weight of theethylene interpolymer sample. The N.A.A. system was calibrated withSpecpure standards (1000 ppm solutions of the desired element (greaterthan 99% pure)). One mL of solutions (elements of interest) werepipetted onto a 15 mm×800 mm rectangular paper filter and air dried. Thefilter paper was then placed in a 1.4 mL polyethylene irradiation vialand analyzed by the N.A.A. system. Standards are used to determine thesensitivity of the N.A.A. procedure (in counts/μg).

Dilution Index (Y_(d)) Measurements

A series of small amplitude frequency sweep tests were run on eachsample using an Anton Paar MCR501 Rotational Rheometer equipped with the“TruGap™ Parallel Plate measuring system”. A gap of 1.5 mm and a strainamplitude of 10% were used throughout the tests. The frequency sweepswere from 0.05 to 100 rad/s at the intervals of seven points per decade.The test temperatures were 170°, 190°, 210° and 230° C. Master curves at190° C. were constructed for each sample using the Rheoplus/32 V3.40software through the Standard TTS (time-temperature superposition)procedure, with both horizontal and vertical shift enabled.

The Y_(d) and X_(d) data generated are summarized in Table 4. The flowproperties of the ethylene interpolymer products, e.g., the meltstrength and melt flow ratio (MFR) are well characterized by theDilution Index (Y_(d)) and the Dimensionless Modulus (X_(d)) as detailedbelow. In both cases, the flow property is a strong function of Y_(d)and X_(d) in addition a dependence on the zero-shear viscosity. Forexample, the melt strength (hereafter MS) values of the disclosedExamples and the Comparative Examples were found to follow the sameequation, confirming that the characteristic VGP point ((√{square rootover (2)})G_(c)*/G_(x)*, δ_(c)) and the derived regrouped coordinates(X_(d), Y_(d)) represent the structure well:MS=a ₀₀ +a ₁₀ log η₀ −a ₂₀(90−δ_(c))−a ₃₀((√{square root over (2)})G_(c) */G _(x)*)−a ₄₀(90−δ_(c))((√{square root over (2)})G _(c) */G_(x)*)

where

a₀₀=−33.33; a₁₀=9.529; a₂₀=0.03517; a₃₀=0.894; a₄₀=0.02969

and r²=0.984 and the average relative standard deviation was 0.85%.

Further, this relation can be expressed in terms of the Dilution Index(Y_(d)) and the Dimensionless Modulus (X_(d)):MS=a ₀ +a ₁ log η₀ +a ₂ Y _(d) +a ₃ X _(d) +a ₄ Y _(d) X _(d)

where

a₀=33.34; a₁=9.794; a₂=0.02589; a₃=0.1126; a₄=0.03307 and

r²=0.989 and the average relative standard deviation was 0.89%.

The MFR of the disclosed Examples and the Comparative samples were foundto follow a similar equation, further confirming that the dilutionparameters Y_(d) and X_(d) show that the flow properties of thedisclosed Examples differ from the reference and Comparative Examples:MFR=b ₀ −b ₁ log η₀ −b ₂ Y _(d) −b ₃ X _(d)

where

-   -   b₀=53.27; b₁=6.107; b₂=1.384; b₃=20.34

and

r²=0.889 and the average relative standard deviation and 3.3%.

Further, the polymerization process and catalyst formulations disclosedherein allow the production of ethylene interpolymer products that canbe converted into flexible manufactured articles that have a uniquebalance of physical properties (i.e. several end-use properties can bebalanced (as desired) through multidimensional optimization); relativeto comparative polyethylenes of comparable density and melt index.

EXAMPLES

Polymerization

The following examples are presented for the purpose of illustratingselected embodiments of this disclosure; it being understood, that theexamples presented do not limit the claims presented.

Examples of the disclosed ethylene interpolymer products were producedin a continuous solution polymerization pilot plant comprising reactorsarranged in series configuration. Methylpentane was used as the processsolvent (a commercial blend of methylpentane isomers). The volume of thefirst CSTR reactor (R1) was 3.2 gallons (12 L), the volume of the secondCSTR reactor (R2) was 5.8 gallons (22 L) and the volume of the tubularreactor (R3) was 4.8 gallons (18 L). Examples of ethylene interpolymerproducts were produced using an R1 pressure from about 14 MPa to about18 MPa; R2 was operated at a lower pressure to facilitate continuousflow from R1 to R2. R1 and R2 were operated in series mode, wherein thefirst exit stream from R1 flows directly into R2. Both CSTR's wereagitated to give conditions in which the reactor contents were wellmixed. The process was operated continuously by feeding fresh processsolvent, ethylene, 1-octene and hydrogen to the reactors.

The single site catalyst components used were: component (i),cyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride,(Cp[(t-Bu)₃PN]TiCl₂), hereafter PIC-1; component (ii), methylaluminoxane(MAO-07); component (iii), trityl tetrakis(pentafluoro-phenyl)borate,and; component (iv), 2,6-di-tert-butyl-4-ethylphenol. The single sitecatalyst component solvents used were methylpentane for components (ii)and (iv) and xylene for components (i) and (iii). The quantity of PIC-1added to R1, “R1 (i) (ppm)” is shown in Table 1A; to be clear, inExample 6 in Table 1A, the solution in R1 contained 0.09 ppm ofcomponent (i), i.e., PIC-1. The mole ratios of the single site catalystcomponents employed to produce Example 6 were: R1 (ii)/(i) moleratio=100, i.e., [(MAO-07)/(PIC-1)]; R1 (iv)/(ii) mole ratio=0, i.e.,[(2,6-di-tert-butyl-4-ethylphenol)/(MAO-07)], and; R1 (iii)/(i) moleratio=1.1, i.e., [(trityl tetrakis(pentafluoro-phenyl)borate)/(PIC-1)].The single site catalyst formulation was injected into R1 using processsolvent, the flow rate of this catalyst containing solvent was about 30kg/hr.

The in-line Ziegler-Natta catalyst formulation was prepared from thefollowing components: component (v), butyl ethyl magnesium; component(vi), tertiary butyl chloride; component (vii), titanium tetrachloride;component (viii), diethyl aluminum ethoxide, and; component (ix),triethyl aluminum. Methylpentane was used as the catalyst componentsolvent. The in-line Ziegler-Natta catalyst formulation was preparedusing the following steps. In step one, a solution of triethylaluminumand dibutylmagnesium ((triethylaluminum)/(dibutylmagnesium) molar ratioof 20) was combined with a solution of tertiary butyl chloride andallowed to react for about 30 seconds (HUT-1); in step two, a solutionof titanium tetrachloride was added to the mixture formed in step oneand allowed to react for about 14 seconds (HUT-2), and; in step three,the mixture formed in step two was allowed to reactor for an additional3 seconds (HUT-3) prior to injection into R2. The in-line Ziegler-Nattaprocatalyst formulation was injected into R2 using process solvent, theflow rate of the catalyst containing solvent was about 49 kg/hr. Thein-line Ziegler-Natta catalyst formulation was formed in R2 by injectinga solution of diethyl aluminum ethoxide into R2. The quantity oftitanium tetrachloride “R2 (vii) (ppm)” added to reactor 2 (R2) is shownin Table 1A; to be clear in Example 6 the solution in R2 contained 3.2ppm of TiCl₄. The mole ratios of the in-line Ziegler-Natta catalystcomponents are also shown in Table 1A, specifically: R2 (vi)/(v) moleratio, i.e., [(tertiary butyl chloride)/(butyl ethyl magnesium)]; R2(viii)/(vii) mole ratio, i.e., [(diethyl aluminum ethoxide)/(titaniumtetrachloride)], and; R2 (ix)/(vii) mole ratio, i.e., [(triethylaluminum)/(titanium tetrachloride)]. To be clear, in Example 6, thefollowing mole ratios were used to synthesize the in-line Ziegler-Nattacatalyst: R2 (vi)/(v) mole ratio=1.98; R2 (viii)/(vii) mole ratio=1.35,and; R2 (ix)/(vii) mole ratio=0.35. Referring to FIG. 1, in all of theExamples disclosed, 100% of the diethyl aluminum ethoxide in stream 10d, component (viii), was added to reactor 12 a via stream 10 h.

In Comparative Example 3, a single site catalyst formulation wasemployed in both reactor 1 and reactor 2. Relative to ComparativeExample 6, the maximum ethylene interpolymer product production rates(kg/h) of Examples 6 and 7, in which a single-site catalyst formulationwas used in R1 and an in-line Ziegler Natta catalyst formulation wasused in R2, were 19% higher (on average). For example, in Example 6(single-site catalyst formulation in R1+in-line Ziegler-Natta catalystin R2) the ethylene interpolymer product was produced at a productionrate of 85.2 kg/h; in contrast, in Comparative Example 3 (single-sitecatalyst formulation in both R1 and R2) the maximum production rate ofthe comparative ethylene interpolymer product was 75.6 kg/h.

Average residence time of the solvent in a reactor is primarilyinfluenced by the amount of solvent flowing through each reactor and thetotal amount of solvent flowing through the solution process, thefollowing are representative or typical values for the examples shown inTables 1A-1C: average reactor residence times were: about 61 seconds inR1, about 73 seconds in R2 and about 50 seconds in R3 (the volume of R3was about 4.8 gallons (18 L)).

Polymerization in the continuous solution polymerization process wasterminated by adding a catalyst deactivator to the third exit streamexiting the tubular reactor (R3). The catalyst deactivator used wasoctanoic acid (caprylic acid), commercially available from P&GChemicals, Cincinnati, Ohio, U.S.A. The catalyst deactivator was addedsuch that the moles of fatty acid added were 50% of the total molaramount of titanium and aluminum added to the polymerization process; tobe clear, the moles of octanoic acid added=0.5×(moles titanium+molesaluminum); this mole ratio was consistently used in all examples.

A two-stage devolitizing process was employed to recover the ethyleneinterpolymer product from the process solvent, i.e., two vapor/liquidseparators were used and the second bottom stream (from the second V/Lseparator) was passed through a gear pump/pelletizer combination. DHT-4V(hydrotalcite), supplied by Kyowa Chemical Industry Co. LTD, Tokyo,Japan was used as a passivator, or acid scavenger, in the continuoussolution process. A slurry of DHT-4V in process solvent was added priorto the first V/L separator. The molar amount of DHT-4V added was about10-fold higher than the molar amount of chlorides added to the process;the chlorides added were titanium tetrachloride and tertiary butylchloride.

Prior to pelletization the ethylene interpolymer product was stabilizedby adding about 500 ppm of Irganox 1076 (a primary antioxidant) andabout 500 ppm of Irgafos 168 (a secondary antioxidant), based on weightof the ethylene interpolymer product. Antioxidants were dissolved inprocess solvent and added between the first and second V/L separators.

Tables 1B and 1C disclose additional solution process parameters, e.g.ethylene and 1-octene splits between the reactors, reactor temperaturesand ethylene conversions, etc. recorded during the production ofExamples 6 and 7 and Comparative Example 3. In Tables 1A-1C the targetedethylene interpolymer product was 0.6 melt index (I₂) (ASTM D1239, 2.16kg load, 190° C.) and 0.915 g/cm³ (ASTM D792). In Comparative Example 3,the single-site catalyst formulation was injected into both reactor R1and R2 and ES^(R1) was 50%. In Example 7, the single site catalystformulation was injected into R1, the in-line Ziegler-Natta catalystformulation was injected into R2 and ES^(R1) was 47%.

FTIR, N.A.A. and Dilution Index analysis was performed on Example 6 withthe following results: 0.038 terminal vinyls/100 C; 5.2 ppm Ti; 4.69Y_(d) (Dilution Index), and; −0.08 X_(d) (Dimensionless Modulus). FTIRand N.A.A. was performed on Example 7 with the following results: 0.042terminal vinyls/100 C, and; 7.7 ppm Ti (Example 7 was not submitted forDilution Index testing).

TABLE 1A Continuous solution process catalyst parameters for: Examples 6and 7 and Comparative Example 3, targeting ethylene interpolymerproducts at 0.60 melt index (I₂ (dg/min)) and a density of 0.915 g/cm³.Com- Exam- Exam- parative Process Parameter ple 6 ple 7 Example 3 R1Catalyst PIC-1 PIC-1 PIC-1 R2 Catalyst ZN ZN PIC-1 R1 (i) (ppm) 0.09 0.10.07 R1 (ii)/(i) mole ratio 100 100 100 R1 (iv)/(ii) mole ratio 0 0 0.3R1 (iii)/(i) mole ratio 1.1 1.1 1.2 R2 (i) (ppm) 0 0 0.14 R2 (ii)/(i)mole ratio 0 0 25 R2 (iv)/(ii) mole ratio 0 0 0.3 R2 (iii)/(i) moleratio 0 0 1.27 R2 (vii) (ppm) 3.2 4.8 0 R2 (vi)/(v) mole ratio 1.98 1.980 R2 (viii)/(vii) mole ratio 1.35 1.35 0 R2 (ix)/(vii) mole ratio 0.350.35 0 Prod. Rate (kg/h) 85.2 94 75.6 Increase in Production Rate 12.724.3 (%)

TABLE 1B Additional solution process parameters for Examples 6-8 andComparative Examples 3 and 4. Exam- Exam- Comparative Process Parameterple 6 ple 7 Example 3 R3 volume (L) 18 18 2.2 ES^(R1) (%) 40 47 50ES^(R2) (%) 60 53 50 ES^(R3) (%) 0 0 0 R1 ethylene concentration (wt %)10.3 10.3 10.3 R2 ethylene concentration (wt %) 13.7 14.9 12.7 R3ethylene concentration (wt %) 13.7 14.9 12.7((1-octene)/(ethylene))^(R1) (wt %) 0.63 0.66 0.81 OS^(R1) (%) 100 10083.3 OS^(R2) (%) 0 0 16.7 OS^(R3) (%) 0 0 0 H₂ ^(R1) (ppm) 0.2 0.2 1.3H₂ ^(R2) (ppm) 1 1 0.8 H₂ ^(R3) (ppm) 0 0 0 Prod. Rate (kg/h) 85.2 9475.6 Increase in Production Rate (%) 12.7 24.3

TABLE 1C Additional solution process parameters for Examples 6-8 andComparative Examples 3 and 4. Exam- Exam- Comparative Process Parameterple 6 ple 7 Example 3 R1 total solution rate (kg/h) 319.9 409.1 369.9 R2total solution rate (kg/h) 280.1 190.9 230.1 R3 solution rate (kg/h) 0 00 Overall total solution rate (kg/h) 600 600 600 R1 inlet temp (° C.) 3030 30 R2 inlet temp (° C.) 30 30 30 R3 inlet temp(° C.) 130 130 130 R1Mean temp (° C.) 140.3 140.1 140.2 R2 Mean temp (° C.) 187.8 202.5 185.7R3 exit temp (actual) (° C.) 198.4 212.1 186 R3 exit temp (calc) (° C.)200.4 215.3 187.6 Q^(R1) (%) 78.2 78.2 78.2 Q^(R2) (%) 80 80 81Q^(R2+R3) (%) 92 92.5 83.7 Q^(R3) (%) 60 62.4 14.1 Q^(T) (%) 94.5 95.290.1 Prod. Rate (kg/h) 85.2 94 75.6 Increase in Production Rate (%) 12.724.3

TABLE 2 Physical properties of Examples 6 and 7 and Comparative Example3. Comparative Property Example 6 Example 7 Example 3 Density (g/cm³)0.9152 0.9155 0.9150 Melt Index I₂ (dg/min) 0.67 0.70 0.58 StressExponent 1.23 1.24 1.27 M_(w) 113893 114401 112210 M_(w)/M_(n) 2.87 3.882.79 CDBI₅₀ 69.0 65.7 74.0

TABLE 3 Computer generated Simulated Example 13: single-site catalystformulation in R1 (PIC-1) and an in-line Ziegler- Natta catalystformulation in R2 and R3. Reactor Reactor Reactor 1 (R1) 2 (R2) 3 (R3)Simulated First Second Third Simulated Physical Ethylene EthyleneEthylene Example Property Interpolymer Interpolymer Interpolymer 13Weight 36.2 56.3 7.5 100 Percent (%) M_(n) 63806 25653 20520 31963 M_(w)129354 84516 67281 99434 M_(z) 195677 198218 162400 195074Polydispersity 2.03 3.29 3.28 3.11 (M_(w)/M_(n)) Branch Frequency 12.611.4 15.6 12.1 (C₆ Branches per 1000C) CDBI₅₀ (%) 90 to 95 55 to 60 45to 55 65 to 70 (range) Density (g/cm³) 0.9087 0.9206 0.9154 0.9169 MeltIndex 0.31 1.92 4.7 1.0 (dg/min)

TABLE 4 Dilution Index (Y_(d)) and Dimensionless Modulus Data (X_(d))for selected embodiments of ethylene interpolymers of this disclosure(Examples), relative to Comparative S, A, D and E. (MFR = melt flow rate(I₂₁/I₂); MS = melt strength) Sample Density MI MS η₀ G⁰N G*_(c) δ_(c)Code [g/cm³] [dg/min] MFR [cN] [kPa · s] [MPa] [kPa] [°] X_(d) Y_(d)Comp. S 0.9176 0.86 29.2 6.46 11.5 1.50 9.43 74.0 0.00 0.02 Comp. A0.9199 0.96 29.6 5.99 10.6 1.17 5.89 80.1 −0.20 3.66 Example 6 0.91520.67 23.7 7.05 12.9 1.57 7.89 79.6 −0.08 4.69 Example 0.9173 0.95 26.35.73 9.67 0.84 7.64 79.0 −0.09 3.93 101 Example 0.9176 0.97 22.6 5.659.38 1.46 7.46 79.5 −0.10 4.29 102 Example 0.9172 0.96 25.3 5.68 9.381.44 7.81 79.3 −0.08 4.29 103 Example 0.9252 0.98 23.9 5.57 9.41 1.648.90 78.1 −0.03 3.8 110 Example 0.9171 0.75 23.4 6.83 12.4 1.48 8.1879.2 −0.06 4.44 115 Example 0.9250 1.04 24.2 5.33 8.81 0.97 8.97 78.9−0.02 4.65 200 Example 0.9165 1.01 27.1 5.43 8.75 0.85 6.75 79.7 −0.153.91 201 Example 0.9204 1.00 24.0 5.99 10.2 1.45 13.5 73.6 0.16 1.82 120Example 0.9232 0.94 22.1 6.21 10.4 0.97 11.6 75.7 0.09 3.02 130 Example0.9242 0.95 22.1 6.24 10.7 1.02 11.6 75.3 0.09 2.59 131 Comp. D 0.92040.82 30.6 7.61 15.4 1.58 10.8 70.4 0.06 −2.77 Comp. E 0.9161 1.00 30.57.06 13.8 1.42 10.4 70.5 0.04 −2.91

TABLE 5A Unsaturation data of several embodiments of the disclosedethylene interpolymers, as well as Comparative B, C, E, E2, G, H, H2, Iand J; as determined by ASTM D3124-98 and ASTM D6248-98. Melt DensityIndex I₂ Melt Flow Stress Unsaturations per 100 C. Sample Code (g/cm³)(dg/min) Ratio (I₂₁/I₂) Exponent Internal Side Chain Terminal Example 110.9113 0.91 24.8 1.24 0.009 0.004 0.037 Example 6 0.9152 0.67 23.7 1.230.008 0.004 0.038 Example 4 0.9154 0.97 37.1 1.33 0.009 0.004 0.047Example 7 0.9155 0.70 25.7 1.24 0.008 0.005 0.042 Example 2 0.9160 1.0427.0 1.26 0.009 0.005 0.048 Example 5 0.9163 1.04 25.9 1.23 0.008 0.0050.042 Example 3 0.9164 0.9 29.2 1.27 0.009 0.004 0.049 Example 53 0.91640.9 29.2 1.27 0.009 0.004 0.049 Example 51 0.9165 1.01 28.0 1.26 0.0090.003 0.049 Example 201 0.9165 1.01 27.1 1.22 0.008 0.007 0.048 Example1 0.9169 0.88 23.4 1.23 0.008 0.005 0.044 Example 52 0.9169 0.85 29.41.28 0.008 0.002 0.049 Example 55 0.9170 0.91 29.8 1.29 0.009 0.0040.050 Example 115 0.9171 0.75 23.4 1.22 0.007 0.003 0.041 Example 430.9174 1.08 24.2 1.23 0.007 0.007 0.046 Comparative E2 0.9138 1.56 24.11.26 0.006 0.007 0.019 Comparative E 0.9144 1.49 25.6 1.29 0.004 0.0050.024 Comparative J 0.9151 4.2 21.8 1.2 0.006 0.002 0.024 Comparative C0.9161 1 30.5 1.35 0.004 0.004 0.030 Comparative B 0.9179 1.01 30.2 1.330.004 0.002 0.025 Comparative H2 0.9189 0.89 30.6 1.36 0.004 0.002 0.021Comparative H 0.9191 0.9 29.6 1.34 0.004 0.003 0.020 Comparative I0.9415 0.87 62 1.61 0.002 0.000 0.025 Comparative G 0.9612 0.89 49 1.580.000 0.000 0.023

TABLE 5B Additional unsaturation data of several embodiments of thedisclosed ethylene interpolymers; as determined by ASTM D3124-98 andASTM D6248-98. Density Melt Index Melt Flow Unsaturations per 100 C.Sample Code (g/cm³) I₂ (dg/min) Ratio (I₂₁/I₂) S. Ex. Internal SideChain Terminal Example 8 0.9176 4.64 27.2 1.25 0.009 0.001 0.048 Example42 0.9176 0.99 23.9 1.23 0.007 0.006 0.046 Example 102 0.9176 0.97 22.61.24 0.007 0.005 0.044 Example 54 0.9176 0.94 29.9 1.29 0.009 0.0020.049 Example 41 0.9178 0.93 23.8 1.23 0.007 0.006 0.046 Example 440.9179 0.93 23.4 1.23 0.007 0.007 0.045 Example 9 0.9190 0.91 40.3 1.380.008 0.003 0.052 Example 200 0.9250 1.04 24.2 1.24 0.006 0.005 0.050Example 60 0.9381 4.57 22.2 1.23 0.005 0.002 0.053 Example 61 0.93964.82 20.2 1.23 0.002 0.002 0.053 Example 62 0.9426 3.5 25.4 1.26 0.0020.002 0.052 Example 70 0.9468 1.9 32.3 1.34 0.001 0.002 0.042 Example 710.9470 1.61 34.8 1.35 0.001 0.001 0.048 Example 72 0.9471 1.51 31.4 1.340.001 0.002 0.043 Example 73 0.9472 1.51 31.6 1.35 0.001 0.002 0.047Example 80 0.9528 1.53 41.1 1.38 0.002 0.000 0.035 Example 81 0.95331.61 50 1.43 0.002 0.000 0.044 Example 82 0.9546 1.6 59.6 1.5 0.0010.000 0.045 Example 90 0.9588 7.51 29 1.28 0.001 0.000 0.042 Example 910.9589 6.72 30.4 1.29 0.002 0.000 0.041 Example 20 0.9596 1.21 31.3 1.350.002 0.001 0.036 Example 21 0.9618 1.31 38.3 1.39 0.002 0.001 0.037Example 22 0.9620 1.3 51 1.49 0.002 0.001 0.041 Example 23 0.9621 0.6378.9 1.68 0.002 0.001 0.042 Example 24 0.9646 1.98 83 1.79 0.001 0.0010.052

TABLE 6A Neutron Activation Analysis (NAA) catalyst residues in severalembodiments of the disclosed ethylene interpolymers, as well asComparatives G, I, J, B, C, E, E2, H and H2. N.A.A. Elemental DensityMelt Index I₂ Analysis (ppm) Sample Code (g/cm³) (dg/min) Ti Mg Cl AlExample 60 0.9381 4.57 9.0 140 284 127 Example 62 0.9426 3.50 9.2 179358 94 Example 70 0.9468 1.90 6.2 148 299 99 Example 71 0.9470 1.61 6.8168 348 87 Example 72 0.9471 1.51 5.8 178 365 88 Example 73 0.9472 1.517.2 142 281 66 Example 80 0.9528 1.53 4.3 141 288 82 Example 81 0.95331.61 6.4 163 332 82 Example 82 0.9546 1.60 5.8 132 250 95 Example 900.9588 7.51 6.7 143 286 94 Example 91 0.9589 6.72 6.7 231 85 112 Example1 0.9169 0.88 6.1 199 99 97 Example 2 0.9160 1.04 7.4 229 104 112Example 3 0.9164 0.90 7.3 268 137 129 Comparative G 0.9612 0.89 1.6 17.253 11 Comparative I 0.9415 0.87 2.3 102 24 53 Comparative J 0.9151 4.201.4 <2 0.6 7.9 Comparative B 0.9179 1.01 0.3 13.7 47 9.3 Comparative C0.9161 1.00 2.0 9.0 25 5.4 Comparative E2 0.9138 1.56 1.2 9.8 32.2 6.8Comparative E 0.9144 1.49 1.3 14.6 48.8 11.3 Comparative H 0.9191 0.902.2 14.6 48.8 11.3 Comparative H2 0.9189 0.89 2.2 253 122 130

TABLE 6B Additional Neutron Activation Analysis (NAA) catalyst residuesin several embodiments of the disclosed ethylene interpolymers. N.A.A.Elemental Density Melt Index I₂ Analysis (ppm) Sample Code (g/cm³)(dg/min) Ti Mg Cl Al Example 4 0.9154 0.97 9.6 287 45 140 Example 50.9163 1.04 6.7 261 70 131 Example 6 0.9152 0.67 5.2 245 48 119 Example7 0.9155 0.70 7.7 365 102 177 Example 8 0.9176 4.64 7.6 234 86 117Example 9 0.9190 0.91 6.4 199 78 99 Example 51 0.9165 1.01 5.9 207 73106 Example 52 0.9169 0.85 5.2 229 104 112 Example 53 0.9164 0.90 7.3347 101 167 Example 54 0.9176 0.94 7.5 295 100 146 Example 55 0.91700.91 7.1 189 101 90 Example 41 0.9178 0.93 7.2 199 103 92 Example 420.9176 0.99 7.5 188 104 86 Example 43 0.9174 1.08 7.4 192 101 91 Example44 0.9179 0.93 7.2 230 121 110 Example 102 0.9176 0.97 9.5 239 60 117Example 115 0.9171 0.75 5.1 258 115 130 Example 61 0.9396 4.82 8.3 35296 179 Example 10 0.9168 0.94 7.8 333 91 170 Example 120 0.9204 1.00 7.3284 75 149 Example 130 0.9232 0.94 5.8 292 114 147 Example 131 0.92420.95 8.6 81.4 173 94 Example 200 0.9250 1.04 6.3 90.1 190 104

What is claimed is:
 1. An ethylene interpolymer product comprising: (i)a first ethylene interpolymer; (ii) a second ethylene interpolymer, and;(iii) optionally a third ethylene interpolymer; wherein said ethyleneinterpolymer product has a Dilution Index, Y_(d), greater than 0; andwherein said first ethylene interpolymer is synthesized using a firstsingle site catalyst formulation; and wherein said second ethyleneinterpolymer is synthesized using a first heterogeneous catalystformulation; and wherein said first single site catalyst formulationcomprises a bulky ligand-metal complex; an aluminoxane cocatalyst; anionic activator and a hindered phenol.
 2. The ethylene interpolymerproduct of claim 1, containing ≤1 part per million (ppm) of a metal A;wherein said metal A originates from said single site catalystformulation used to synthesize said first ethylene interpolymer.
 3. Theethylene interpolymer product of claim 2; wherein said metal A istitanium, zirconium or hafnium.
 4. The ethylene interpolymer product ofclaim 1 having a metal B and optionally a metal C and the total amountof said metal B plus said metal C is from about 3 to about 11 parts permillion; wherein said metal B originates from said first heterogeneouscatalyst formulation used to synthesize said second ethyleneinterpolymer and optionally said metal C originates from a secondheterogeneous catalyst formulation used to synthesize said thirdethylene interpolymer; optionally said metal B and said metal C are thesame metal.
 5. The ethylene interpolymer product of claim 4; whereinsaid metal B and said metal C, are independently selected from titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum,tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium. 6.The ethylene interpolymer product of claim 4; wherein said metal B andsaid metal C, are independently selected from titanium, zirconium,hafnium, vanadium or chromium.
 7. The ethylene interpolymer product ofclaim 1 wherein said first ethylene interpolymer has a first Mw/Mn, saidsecond ethylene interpolymer has a second Mw/Mn and said optional thirdethylene interpolymer has a third Mw/Mn; wherein said first Mw/Mn islower than said second Mw/Mn and said optional third Mw/Mn.
 8. Theethylene interpolymer product of claim 7; wherein the blending of saidsecond ethylene interpolymer and said third ethylene interpolymer formsa heterogeneous ethylene interpolymer blend having a fourth Mw/Mn;wherein said fourth Mw/Mn is not broader than said second Mw/Mn.
 9. Theethylene interpolymer product of claim 7 wherein said second Mw/Mn andsaid optional third Mw/Mn are ≤4.0.
 10. The ethylene interpolymerproduct of claim 1; wherein said first ethylene interpolymer has a firstCDBI₅₀ from about 70 to about 98%, said second ethylene interpolymer hasa second CDBI₅₀ from about 45 to about 98% and said optional thirdethylene interpolymer has a third CDBI₅₀ from about 35 to about 98%. 11.The ethylene interpolymer product of claim 10; wherein said first CDBI₅₀is higher than said second CDBI₅₀; optionally said first CDBI₅₀ ishigher than said third CDBI₅₀.
 12. The ethylene interpolymer product ofclaim 1; wherein (i) said first ethylene interpolymer is from about 15to about 60 weight percent of said ethylene interpolymer product; (ii)said second ethylene interpolymer is from about 30 to about 85 weightpercent of said ethylene interpolymer product, and; (iii) optionallysaid third ethylene interpolymer is from about 0 to about 30 weightpercent of said ethylene interpolymer product; wherein weight percent isthe weight of said first, said second or said optional third ethyleneinterpolymer divided by the weight of said ethylene interpolymerproduct.
 13. The ethylene interpolymer product of claim 1; wherein (i)said first ethylene interpolymer has a melt index from about 0.01 toabout 200 dg/minute; (ii) said second ethylene interpolymer has meltindex from about 0.3 to about 1000 dg/minute, and; (iii) optionally saidthird ethylene interpolymer has a melt index from about 0.5 to about2000 dg/minute; wherein melt index is measured according to ASTM D1238(2.16 kg load and 190° C.).
 14. The ethylene interpolymer product ofclaim 1; wherein (i) said first ethylene interpolymer has a density fromabout 0.855 g/cc to about 0.975 g/cc; (ii) said second ethyleneinterpolymer has a density from about 0.89 g/cc to about 0.975 g/cc,and; (iii) optionally said third ethylene interpolymer has density fromabout 0.89 g/cc to about 0.975 g/cc; wherein density is measuredaccording to ASTM D792.
 15. The ethylene interpolymer product of claim 1synthesized using a solution polymerization process.
 16. The ethyleneinterpolymer product of claim 1 further comprising from 0 to about 10mole percent of one or more α-olefins.
 17. The ethylene interpolymerproduct of claim 16; wherein said one or more α-olefin are C₃ to C₁₀α-olefins.
 18. The ethylene interpolymer product of claim 17; whereinsaid one or more α-olefin is 1-hexene, 1-octene or a mixture of 1-hexeneand 1-octene.
 19. The ethylene interpolymer product of claim 1 whereinsaid alumoxane is methyl alumoxane.
 20. The ethylene interpolymerproduct of claim 19 where the molar ratio of said hindered phenol/saidalumoxane is from 0.1/1 to 10/1.